Apparatus and process for plasma-enhanced atomic layer deposition

ABSTRACT

Embodiments of the invention provide an apparatus configured to form a material during an atomic layer deposition (ALD) process, such as a plasma-enhanced ALD (PE-ALD) process. In one embodiment, a showerhead assembly comprises a showerhead and a plasma baffle that are used to disperse process gases within a plasma-enhanced vapor deposition chamber. The showerhead plate comprises an inner area configured to position the plasma baffle therein and an outer area which has a plurality of holes for emitting a process gas. The plasma baffle comprises a conical nose disposed on an upper surface to receive another process gas, a lower surface to emit the process gas and a plurality of openings configured to flow the process gas from above the upper surface into a process region. The openings are preferably slots that are positioned at predetermined angle for emitting the process gas with a circular flow pattern.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims benefit of co-pending U.S. Ser. No. 60/733,870(10429L), filed Nov. 4, 2005, U.S. Ser. No. 60/733,655 (10429L.02),filed Nov. 4, 2005, U.S. Ser. No. 60/733,654 (10429L.03), filed Nov. 4,2005, U.S. Ser. No. 60/733,574 (10429L.04), filed Nov. 4, 2005, and U.S.Ser. No. 60/733,869 (10429L.05), filed Nov. 4, 2005, which are allincorporated herein by reference in their entirety.

BACKGROUND OF THE INVENTION

1. Field of the Invention

Embodiments of the invention generally relate to an apparatus and amethod for depositing materials, and more particularly to an atomiclayer deposition chamber configured to deposit a material during aplasma-enhanced process.

2. Description of the Related Art

In the field of semiconductor processing, flat-panel display processingor other electronic device processing, vapor deposition processes haveplayed an important role in depositing materials on substrates. As thegeometries of electronic devices continue to shrink and the density ofdevices continues to increase, the size and aspect ratio of the featuresare becoming more aggressive, e.g., feature sizes of 0.07 μm and aspectratios of 10 or greater. Accordingly, conformal deposition of materialsto form these devices is becoming increasingly important.

While conventional chemical vapor deposition (CVD) has proved successfulfor device geometries and aspect ratios down to 0.15 μm, the moreaggressive device geometries require an alternative depositiontechnique. One technique that is receiving considerable attention isatomic layer deposition (ALD). During an ALD process, reactant gases aresequentially introduced into a process chamber containing a substrate.Generally, a first reactant is pulsed into the process chamber and isadsorbed onto the substrate surface. A second reactant is pulsed intothe process chamber and reacts with the first reactant to form adeposited material. A purge step is typically carried out between thedelivery of each reactant gas. The purge step may be a continuous purgewith the carrier gas or a pulse purge between the delivery of thereactant gases. Thermally induced ALD processes are the most common ALDtechnique and use heat to cause the chemical reaction between the tworeactants. While thermal ALD processes work well to deposit somematerials, the processes often have a slow deposition rate. Therefore,fabrication throughput may be impacted to an unacceptable level. Thedeposition rate may be increased at a higher deposition temperature, butmany chemical precursors, especially metal-organic compounds, decomposeat elevated temperatures.

The formation of materials by plasma-enhanced ALD (PE-ALD) processes isalso a known technique. In some examples of PE-ALD processes, a materialmay be formed from the same chemical precursors as a thermal ALDprocess, but at a higher deposition rate and a lower temperature.Although several variations of techniques exist, in general, a PE-ALDprocess provides that a reactant gas and a reactant plasma aresequentially introduced into a process chamber containing a substrate.The first reactant gas is pulsed into the process chamber and isadsorbed onto the substrate surface. Thereafter, the reactant plasma ispulsed into the process chamber and reacts with the first reactant gasto form a deposited material. Similarly to a thermal ALD process, apurge step may be conducted between the delivery of each of thereactants. While PE-ALD processes overcome some of the shortcomings ofthermal ALD processes due to the high degree of reactivity of thereactant radicals within the plasma, PE-ALD processes have manylimitations. PE-ALD process may cause plasma damage to a substrate(e.g., etching), be incompatible with certain chemical precursors andrequire additional hardware.

Therefore, there is a need for an apparatus and a process for depositingor forming a material on a substrate by a vapor deposition technique,preferably by a plasma-enhanced technique, and more preferably, by aPE-ALD technique.

SUMMARY OF THE INVENTION

Embodiments of the invention provide an apparatus configured to form amaterial during an atomic layer deposition (ALD) process, such as aplasma-enhanced ALD (PE-ALD) process. In one embodiment, a processchamber is configured to expose a substrate to a sequence of gases andplasmas during a PE-ALD process. The process chamber contains componentsthat are capable of being electrically insulated, electrically groundedor RF energized. In one example, a chamber body and a gas manifoldassembly are grounded and separated by electrically insulatedcomponents, such as an insulation cap, a plasma screen insert and anisolation ring. A showerhead, a plasma baffle and a water box arepositioned between the insulated components and become RF hot whenactivated by a plasma generator.

In one example, a chamber for processing substrates is provided whichincludes a substrate support having a substrate receiving surface and achamber lid assembly with a process region contained therebetween. Inone embodiment, the chamber lid assembly contains a showerhead assemblyhaving an inner region and an outer region, a cooling assembly incontact with the showerhead assembly, a plasma baffle disposed withinthe inner region of the showerhead assembly, a plasma screen disposedabove the showerhead assembly and configured to direct a first processgas to the plasma baffle and a second process gas to the outer region ofthe showerhead assembly, a first gas region located between the plasmabaffle and the plasma screen and a second gas region located between theouter region of the showerhead assembly and the cooling assembly.

In another example, a chamber for processing substrates is providedwhich includes a substrate support having a substrate receiving surfaceand a chamber lid that contains a channel at a central portion of thechamber lid. A tapered bottom surface extending from the channel to aplasma screen disposed above a plasma baffle and a showerhead, whereinthe showerhead is shaped and sized to substantially cover the substratereceiving surface, a first conduit coupled to a first gas inlet withinthe channel and a second conduit coupled to a second gas inlet withinthe channel, wherein the first conduit and the second conduit arepositioned to provide a gas flow in a circular direction.

In another example, a chamber for processing substrates is providedwhich includes a substrate support having a substrate receiving surface,a chamber lid assembly contains a showerhead assembly having an innerregion and an outer region, a plasma screen disposed above theshowerhead assembly and configured to direct a first process gas to theinner region and a second process gas to the outer region and a processregion situated between the substrate receiving surface and the chamberlid assembly. The plasma screen contains an inner area for receiving thefirst process gas and an outer area for receiving the second processgas.

In another embodiment, a lid assembly is configured to expose asubstrate to a sequence of gases and plasmas during a PE-ALD process.The lid assembly contains components that are capable of beingelectrically insulated, electrically grounded or RF energized. In oneexample, the lid assembly contains a grounded gas manifold assemblypositioned above electrically insulated components, such as aninsulation cap, a plasma screen insert and an isolation ring. Ashowerhead, a plasma baffle and a water box are positioned between theinsulated components and become RF hot when activated by a plasmagenerator.

In one example, the showerhead assembly contains a showerhead platehaving a lower surface to substantially cover the substrate receivingsurface. The inner region of the showerhead assembly contains the plasmabaffle as a removable component. The showerhead assembly and the plasmabaffle usually contain a conductive material, such as aluminum,stainless steel, steel, iron, chromium, nickel, alloys thereof orcombinations thereof. Also, the lower surface of the showerhead plateand the plasma baffle are positioned parallel or substantially parallelto the substrate receiving surface and are connected to an electricalsource for igniting a plasma. The outer region of the showerheadassembly contains a plurality of holes in fluid communication with theprocess region. Each of the holes may have a diameter within a rangefrom about 0.20 mm to about 0.80 mm, preferably, from about 0.40 mm toabout 0.60 mm, such as about 0.51 mm. The showerhead plate may containabout 1,000 holes or more, such as about 1,500 holes or more. The holeshave a diameter to prohibit back diffusion of gas or to prohibitformation of a secondary plasma.

In another example, a lid assembly for conducting a vapor depositionprocess within a process chamber is provided which includes aninsulation cap containing a first channel configured to flow a firstprocess gas and a plasma screen having an upper surface with an innerarea and an outer area. The insulation cap may be positioned on theupper surface of the plasma screen. A first plurality of openings withinthe inner area of the plasma screen is configured to direct the firstprocess gas from above the upper surface to below a lower surface and asecond plurality of openings within the outer area of the plasma screenis configured to flow a second process gas from above the upper surfaceto below the lower surface. In one example, the first plurality ofopenings contains holes and the second plurality of openings containsslots. Also, the insulation cap may contain a second channel configuredto flow the second process gas to the outer area of the plasma screen.The inner area of the plasma screen contains a zone free of holes and afirst flow pattern of the first process gas is directional at aline-of-sight to the zone. The line-of-sight of the first flow patternis directional obscure to the plurality of holes so to prohibit asecondary plasma from igniting above the upper surface of the plasmascreen. In one example, each of the holes have a diameter within a rangefrom about 0.5 mm to about 5 mm, preferably, from about 1 mm to about 3mm, and more preferably, about 1.5 mm. The plurality of holes maycontain at least about 100 holes, preferably at least about 150 holes.The insulation cap and the plasma screen may each be formed from amaterial that is electrically insulating, thermally insulating orelectrically and thermally insulating, such as a ceramic material, aquartz material or a derivative thereof.

In another embodiment, a showerhead assembly contains a showerhead and aplasma baffle for dispersing process gases within a plasma-enhancedvapor deposition chamber. The showerhead plate contains an inner areaconfigured to position the plasma baffle therein and an outer area whichhas a plurality of holes for emitting a process gas. The plasma bafflecontains a conical nose disposed on an upper surface to receive anotherprocess gas, a lower surface to emit the process gas and a plurality ofopenings configured to flow the process gas from above the upper surfaceinto a process region. The openings are preferably slots that arepositioned at predetermined angle for emitting the process gas with acircular flow pattern.

In one example, the plasma baffle assembly contains a plurality of slotsextending from the first gas region through the assembly to providefluid communication from the first gas region into the process region.The plasma baffle assembly further contains a nose cone extending froman upper surface of the plasma baffle to a lower surface of the plasmascreen. The slots extend across the upper surface between the nose coneand an outer edge of the assembly at a tangential angle from a centerportion. Each slot is extended through the plasma baffle assembly at apredetermined injection angle relative to the substrate receivingsurface. The predetermined injection angle may be within a range fromabout 20° to about 700, preferably, from about 30° to about 600, andmore preferably, from about 40° to about 500, such as about 45°. Eachslot of the plurality of slots may have a width within a range fromabout 0.60 mm to about 0.90 mm, preferably, from about 0.70 mm to about0.80 mm, such as about 0.76 mm and may have a length within a range fromabout 10 mm to about 50 mm, preferably, from about 20 mm to about 30 mm,such as about 23 mm or more. The plasma baffle assembly usually containsabout 10 slots or more, such as about 20 slots or more. The slots have awidth to prohibit back diffusion of gas or to prohibit formation of asecondary plasma. In one example, the upper surface of the plasma baffleis directed downwardly way from the nose cone. The upper surface mayangled in order receive a process gas through openings of the slots anddisperse the process gas with a uniform flow rate.

In another example, a plasma baffle assembly for receiving a process gaswithin a plasma-enhanced vapor deposition chamber is provided whichincludes a plasma baffle plate containing an upper surface to receive aprocess gas and a lower surface to emit the process gas. The plasmabaffle assembly contains a plurality of openings configured to flow theprocess gas from above the upper surface to below the lower surface,wherein each opening is positioned at an obscured angle or at apredetermined angle, measured from a perpendicular axis of the lowersurface.

In another example, the cooling assembly contains a plurality ofpassageways for the second process gas to pass into the second gasregion. The plurality of passageways provides fluid communication fromthe plasma screen to the second gas region. The plurality of passagewayscontains at least about 10 channels, preferably, at least about 20channels, and more preferably, at least about 30 channels, such as about36 channels.

In another example, a showerhead assembly for conducting a vapordeposition process is provided which includes a showerhead plate havinga bottom surface to substantially cover a substrate receiving surfacewithin a process chamber, an inner region of the showerhead plate fordistributing a first process gas through a plurality of slots positionedat a predetermined injection angle relative to the substrate receivingsurface and an outer region of the showerhead plate for distributing asecond process gas through a plurality of holes.

In another example, a showerhead assembly for receiving a process gaswithin a plasma-enhanced vapor deposition chamber is provided whichincludes a showerhead plate containing an upper surface to receive gasesand a lower surface to emit the gases. An inner area on the uppersurface for receiving a first process gas contains a first plurality ofopenings configured to flow the first process gas from above the uppersurface to below the lower surface. An outer area on the upper surfacefor receiving the second process gas contains a second plurality ofopenings configured to flow the second process gas from above the uppersurface to below the lower surface. For example, a cooling assembly maybe positioned above and in contact with the showerhead plate. An innerregion is formed between the inner area and the cooling assembly and anouter region is formed between the outer area and the cooling assembly.The inner region of the showerhead plate may contain a plasma baffle.

In another example, a cooling assembly contains a plurality ofpassageways for directing a second process gas into the outer region.Each passageway of the plurality of passageways extends into the outerregion at a predetermined angle. The predetermined angle may prohibitback diffusion of gas or formation of a secondary plasma. In oneexample, the predetermined angle may be within a range from about 5° toabout 850, preferably, from about 10° to about 45°, and more preferably,from about 15° to about 350. Each passageway of the plurality ofpassageways may provide an obscured flow path for the second process gasinto the outer region. In one example, the cooling assembly may haveabout 36 passageways.

In another embodiment, a lid assembly for conducting a vapor depositionprocess within a process chamber is provided which includes aninsulation cap and a plasma screen. In one example, the insulation caphas a centralized channel configured to flow a first process gas from anupper surface to an expanded channel and an outer channel configured toflow a second process gas from an upper surface to a groove which isencircling the expanded channel. In one example, the plasma screen hasan upper surface containing an inner area with a plurality of holes andan outer area with a plurality of slots. The insulation cap may bepositioned on top of the plasma screen to form a centralized gas regionwith the expanded channel and a circular gas region with the groove.

In another example, an insulating cap is positioned above the plasmascreen. The insulating cap contains at least two gas passageways, suchthat a first gas passageway is positioned to direct the first processgas to an inner region of the plasma screen and a second gas passagewayis positioned to direct the second process gas to an outer region of theplasma screen. The insulating cap contains an electrically insulatingmaterial, such as a ceramic material, a quartz material or a derivativethereof.

In another example, a gas manifold is disposed above the insulating capand contains at least two gas passageways. A first gas passageway ispositioned to provide the first process gas to the insulating cap and asecond gas passageway is positioned to provide the second process gas tothe insulating cap. A first conduit and a second conduit may be coupledto the first gas passageway and are positioned to provide the firstprocess gas a gas flow in a circular direction. The first conduit andthe second conduit are independently positioned to direct gas at aninner surface of the first gas passageway. The gas flow usually has thecircular direction with a geometry of a vortex, a helix, a spiral, aswirl, a twirl, a twist, a coil, a corkscrew, a curl, a whirlpool, orderivatives thereof. The first conduit and the second conduit areindependently positioned at an angle from a center axis of the first gaspassageway. The angle may be greater than 0°, preferably, greater thanabout 20°, and more preferably, greater than about 35°. A valve may becoupled between the first conduit and a precursor source to enable anALD process with a pulse time of about 10 seconds or less, preferably,about 6 seconds or less, and more preferably, about 1 second or less,such as within a range from about 0.01 seconds to about 0.5 seconds.

In another example, a capping assembly for conducting a vapor depositionprocess within a process chamber is provided which includes aninsulation cap containing an upper surface configured to receive agrounded gas manifold, a first channel configured to flow a firstprocess gas from the upper surface to a lower surface of the insulationcap and a second channel configured to flow a second process gas fromthe upper surface to the lower surface. The lower surface may furthercontain an inner region and an outer region, such that the first channelis in fluid communication with the inner region and the second channelis in fluid communication with the outer region. In one example, theinner region contains an expanding channel. The expanding channel mayhave an inner diameter within a range from about 0.5 cm to about 7 cm,preferably, from about 0.8 cm to about 4 cm, and more preferably, fromabout 1 cm to about 2.5 cm. Also, the expanding channel may contain anouter diameter within a range from about 2 cm to about 15 cm,preferably, from about 3.5 cm to about 10 cm, and more preferably, fromabout 4 cm to about 7 cm.

In another example, a plasma screen assembly for receiving a process gaswithin a plasma-enhanced vapor deposition chamber is provided whichincludes a plasma screen containing an upper surface to receive gasesand a lower surface to emit the gases, an inner area on the uppersurface for receiving a first process gas, wherein the inner areacontains a first plurality of openings configured to flow the firstprocess gas from above the upper surface to below the lower surface, andan outer area on the upper surface for receiving the second process gas,wherein the outer area contains a second plurality of openingsconfigured to flow the second process gas from above the upper surfaceto below the lower surface. The inner area further contains a zone freeof the plurality of openings and a first flow pattern of the firstprocess gas is directional at a line-of-sight to the zone, so to bedirectional obscure to the plurality of openings.

In another example, the plasma screen assembly contains an inner areafor receiving the first process gas and an outer area for receiving thesecond process gas. The inner area of the plasma screen assemblycontains a plurality of holes for directing the first process gas to theplasma baffle assembly. Each hole may have a diameter within a rangefrom about 0.5 mm to about 5 mm preferably, from about 1 mm to about 3mm, such as about 1.5 mm. The outer area of the plasma screen contains aplurality of slots for directing the second process gas into the secondgas region. The slots may be parallel or substantially parallel to asubstrate receiving surface or the slots may be perpendicular orsubstantially perpendicular to the plurality of holes within the firstarea of the plasma screen. Each slot may have a width within a rangefrom about 0.20 mm to about 0.80 mm, preferably, from about 0.40 mm toabout 0.60 mm, such as about 0.51 mm. The plasma screen assemblycontains at least about 10 slots, preferably about 36 slots or more.Also, the plasma screen assembly is formed from an electricallyinsulating material, such as a ceramic material, a quartz material or aderivative thereof.

In another example, a plasma screen assembly for receiving a process gaswithin a plasma-enhanced vapor deposition chamber is provided whichincludes an upper surface to receive gases and a lower surface to emitthe gases. An inner area on the upper surface for receiving a firstprocess gas contains a first plurality of openings configured to flowthe first process gas from above the upper surface to below the lowersurface. An outer area on the upper surface for receiving the secondprocess gas contains a second plurality of openings configured to flowthe second process gas from above the upper surface to below the lowersurface.

Embodiments of the invention also provide a method for forming amaterial on a substrate during a thermal ALD process and a PE-ALDprocess. In another embodiment, a method is provided which includesflowing at least one process gas through at least one conduit to form acircular gas flow pattern, exposing a substrate to the circular gas flowpattern, sequentially pulsing at least one chemical precursor into theprocess gas and igniting a plasma from the process gas to deposit amaterial on the substrate. In one example, the circular gas flow patternhas circular geometry of a vortex, a helix, a spiral, a swirl, a twirl,a twist, a coil, a corkscrew, a curl, a whirlpool, or derivativesthereof. Materials that may be deposited by the method includeruthenium, tantalum, tantalum nitride, tungsten, or tungsten nitride.

In another example, a method for depositing a material on a substrate isprovided which includes positioning a substrate on a substrate supportwithin a process chamber containing a chamber lid assembly, flowing atleast one carrier gas through at least one conduit to form a circulargas flow pattern, exposing the substrate to the circular gas flowpattern, pulsing at least one precursor into the at least one carriergas and depositing a material containing at least one element from theat least one precursor onto the substrate. The chamber lid assembly maycontain a showerhead assembly having an inner region and an outerregion, a plasma screen disposed above the showerhead assembly andconfigured to direct a first process gas to the inner region and asecond process gas to the outer area, a first gas region located abovethe inner region and between the showerhead assembly and the plasmascreen and a second gas region located above the outer region.

In another example, a method for depositing a material on a substrate isprovided which includes positioning a substrate on a substrate supportwithin a process chamber containing a gas delivery system capable offorming a gas flow in a circular direction, flowing at least one carriergas into the process chamber to form a circular gas flow pattern andexposing the substrate to the circular gas flow pattern during aplasma-enhanced atomic layer deposition process comprising sequentiallyigniting a plasma and pulsing at least one precursor into the at leastone carrier gas to deposit a material onto the substrate.

In another example, a method for forming a ruthenium material on asubstrate is provide which includes positioning a substrate within aplasma-enhanced process chamber containing a showerhead, a plasma baffleand a plasma screen and exposing the substrate sequentially to apyrrolyl ruthenium precursor and a reagent during an ALD process whileforming a ruthenium material on the substrate. The pyrrolyl rutheniumprecursor contains ruthenium and at least one pyrrolyl ligand with thechemical formula of:

wherein R₁, R₂, R₃, R₄ and R₅ are each independently selected fromhydrogen or an organic group, such as methyl, ethyl, propyl, butyl,amyl, derivatives thereof or combinations thereof. In one example, eachR₂, R₃, R₄ and R₅ is either a hydrogen group or a methyl group. Inanother example, each R₂ and R₅ is a methyl group or an ethyl group.

The method further provides that the pyrrolyl ruthenium precursor maycontain a first pyrrolyl ligand and a second pyrrolyl ligand, such thatthe first pyrrolyl ligand may be the same as or different than thesecond pyrrolyl ligand. Alternatively, the pyrrolyl ruthenium precursormay contain a first pyrrolyl ligand and a dienyl ligand. For example,the pyrrolyl ruthenium precursor may be a pentadienyl pyrrolyl rutheniumprecursor, a cyclopentadienyl pyrrolyl ruthenium precursor, analkylpentadienyl pyrrolyl ruthenium precursor or analkylcyclopentadienyl pyrrolyl ruthenium precursor. Therefore, themethod provides that the pyrrolyl ruthenium precursor may be an alkylpyrrolyl ruthenium precursor, a bis(pyrrolyl) ruthenium precursor, adienyl pyrrolyl ruthenium precursor, or derivatives thereof. Someexemplary pyrrolyl ruthenium precursors include bis(tetramethylpyrrolyl)ruthenium, bis(2,5-dimethylpyrrolyl) ruthenium, bis(2,5-diethylpyrrolyl)ruthenium, bis(tetraethylpyrrolyl) ruthenium, pentadienyltetramethylpyrrolyl ruthenium, pentadienyl 2,5-dimethylpyrrolylruthenium, pentadienyl tetraethylpyrrolyl ruthenium, pentadienyl2,5-diethylpyrrolyl ruthenium, 1,3-dimethylpentadienyl pyrrolylruthenium, 1,3-diethylpentadienyl pyrrolyl ruthenium,methylcyclopentadienyl pyrrolyl ruthenium, ethylcyclopentadienylpyrrolyl ruthenium, 2-methylpyrrolyl pyrrolyl ruthenium, 2-ethylpyrrolylpyrrolyl ruthenium, and derivatives thereof.

In another example, a method for forming a ruthenium material on asubstrate is provide which includes positioning a substrate within aplasma-enhanced process chamber containing a showerhead, a plasma baffleand a plasma screen and exposing the substrate sequentially to an activereagent and a pyrrolyl ruthenium precursor during a PE-ALD process.Although a plasma may be ignited during any time period of the PE-ALDprocess, preferably, the plasma is ignited while the reagent is exposedto the substrate. The plasma activates the reagent to form an activereagent. Examples of an active reagent include an ammonia plasma, anitrogen plasma and a hydrogen plasma. One embodiment of the PE-ALDprocess provides that the plasma is generated external from the processchamber, such as by a remote plasma generator (RPS) system. However, apreferred embodiment of the PE-ALD process provides that the plasma isgenerated in situ by a plasma capable process chamber utilizing a radiofrequency (RF) generator.

In another example, a method for forming a ruthenium material on asubstrate is provide which includes positioning a substrate within aplasma-enhanced process chamber containing a showerhead, a plasma baffleand a plasma screen and exposing the substrate sequentially to a reagentand a pyrrolyl ruthenium precursor during a thermal-ALD process. Theruthenium material may be deposited on a barrier layer (e.g., copperbarrier) or dielectric material (e.g., low-k) disposed on the substrateduring the various ALD processes described herein. The barrier layer maycontain a material that includes tantalum, tantalum nitride, tantalumsilicon nitride, titanium, titanium nitride, titanium silicon nitride,tungsten or tungsten nitride. In one example, the ruthenium material isdeposited on a tantalum nitride material previously formed by an ALDprocess or a PVD process. The dielectric material may include silicondioxide, silicon nitride, silicon oxynitride, carbon-doped siliconoxides or a SiO_(x)C_(y) material.

A conductive metal may be deposited on the ruthenium material. Theconductive material may contain copper, tungsten, aluminum, an alloythereof or a combination thereof. In one aspect, the conductive metalmay be formed as one layer during a single deposition process. Inanother aspect, the conductive metal may be formed as multiple layers,each deposited by an independent deposition process. In one embodiment,a seed layer is deposited on the ruthenium material by an initialdeposition process and a bulk layer is subsequently deposited thereon byanother deposition process. In one example, a copper seed layer isformed by an electroless deposition process, an electroplating (ECP)process or a PVD process and a copper bulk layer is formed by anelectroless deposition process, an ECP process or a CVD process. Inanother example, a tungsten seed layer is formed by an ALD process or aPVD process and a tungsten bulk layer is formed by a CVD process or aPVD process.

BRIEF DESCRIPTION OF THE DRAWINGS

So that the manner in which the above recited features of the inventionare attained and can be understood in detail, a more particulardescription of the invention, briefly summarized above, may be had byreference to the embodiments thereof which are illustrated in theappended drawings. It is to be noted, however, that the appendeddrawings illustrate only typical embodiments of this invention and aretherefore not to be considered limiting of its scope, for the inventionmay admit to other equally effective embodiments.

FIGS. 1A-1G illustrate schematic views of a process chamber as describedin an embodiment herein;

FIGS. 2A-2B illustrate a schematic view of an isolation ring asdescribed in an embodiment herein;

FIGS. 3A-3B illustrate schematic views of a showerhead as described inan embodiment herein;

FIGS. 4A-4F illustrate schematic views of a water box as described in anembodiment herein;

FIGS. 5A-5F illustrate schematic views of plasma baffle inserts asdescribed in embodiments herein;

FIGS. 6A-6B illustrate schematic views of a plasma screen insert asdescribed in an embodiment herein;

FIGS. 7A-7C illustrate schematic views of an insulation cap insert asdescribed in an embodiment herein;

FIGS. 8A-8D illustrate schematic views of a gas manifold assembly asdescribed in an embodiment herein;

FIGS. 9A-9D illustrate schematic views of a gas flows described in anembodiment herein; and

FIGS. 10A-10C illustrate alternative schematic views of a gas flows asdescribed in an embodiment herein.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

Embodiments of the invention provide an apparatus configured to deposita material during a thermal atomic layer deposition (ALD) process, orpreferably, during a plasma-enhance ALD (PE-ALD) process. Otherembodiments of the invention provide processes for forming the materialwithin the process chamber. In one embodiment, a process chamber isconfigured to perform a PE-ALD process and has multiple components thatare electrically insulated, electrically grounded or RF hot. In oneexample, a chamber body and gas manifold assembly are grounded andseparated by electrically insulated components, such as an isolationring, a plasma screen insert and an insulation cap. A showerhead, aplasma baffle and a water box are disposed between the electricallyinsulated components and are RF hot when activated by a plasmagenerator.

Hardware

FIGS. 1A-1G illustrate schematic views of lid assembly 100 that may beused to perform a variety of ALD processes. In one embodiment, processchamber 50 may be used to form materials on substrate 8 during a thermalALD process or a PE-ALD process. FIG. 1A depicts a schematiccross-sectional view of process chamber 50 that may be used to performintegrated circuit fabrication. Process chamber 50 contains lid assembly100 attached to chamber body assembly 90. Process region 60 forsubstrate processing is formed and generally situated between lidassembly 100 and chamber body assembly 90, and more specifically, justabove support surface 41 of substrate support 40 and substrate 8 andjust below upper surface 62. In one embodiment, the chamber spacingbetween upper surface 62 and support surface 41 is within a range fromabout 0.50 mm to about 50.00 mm, preferably, from about 1.00 mm to about12.00 mm, and more preferably, from about 4.00 mm to about 8.00 mm, suchas 5.84 mm (0.230 in). The spacing may vary depending on the gases beingdelivered and the process conditions during a deposition process.

Substrate support 40 contains edge ring 44 and heating element 45 (FIGS.1A and 1G). Heating element 45 is embedded within substrate support 40.Edge ring 44 is circumferentially disposed around substrate support 40and over an upper portion of substrate support 40. Inner edge rings 48a, 48 b and 48 c are situated on heating element 45 and below thesegment of edge ring 44 which covers the upper portion of substratesupport 40. Edge ring 44 may be used as a purge ring by allowing an edgepurge gas to flow from substrate support 40, through gap 47, betweeninner edge rings 48 a, 48 b and 48 c, edge ring 44 and heating element45 and over the edge of substrate 8 (FIG. 1G). The flow of the edgepurge gas prevents reactive process gasses from diffusing into heatingelement 45.

Choke gap 61 is a circumferential gap or space formed between edge ring44 and upper surface 62, more specifically, between the top edge surfaceof edge ring 44 and lower surface 202 d of isolation ring 200. Choke gap61 also helps provide a more uniform pressure distribution withinprocess region 60 by partially separating process region 60 from thenon-uniform pressure distribution of interior chamber region 59. Chokegap 61 may be varied depending on the process conditions and therequired pumping efficiency. The pumping efficiency during a depositionprocess may be controlled by adjusting choke gap 61. Choke gap 61 isincreased by lowering substrate support 40 or decreased by raisingsubstrate support 40. The pumping conductance from the pumping port 38in the lower portion of process chamber 50 to the center of channel 820is modified by changing the distance of choke gap 61 to control thethickness and the uniformity of a film during deposition processesdescribed herein. In one embodiment, the spacing of upper choke gap 61is within a range from about 0.50 mm to about 50.00 mm, preferably, fromabout 1.00 mm to about 5.00 mm, and more preferably, from about 2.5 mmto about 4 mm, such as 3.30 mm (0.130 in).

In one embodiment, the pressure differentials of the pumping conductancemay be controlled in order to reduce or eliminate the formation ofsecondary plasmas. Since the generation and sustainability of a plasmais ion concentration dependant, the pressure within a particular regionmay be reduced to minimize the ion concentration. Therefore, a secondaryplasma may be avoided within a desired region of the process chamber. Ina preferred embodiment, process chamber 50 is configured to conduct aPE-ALD process. Therefore, various regions and components throughoutprocess chamber 50 are electrically insulated, electrically grounded orRF hot. In one example, chamber body 80 and gas manifold assembly 800are grounded and separated by electrically insulated isolation ring 200,plasma screen insert 600 and insulation cap 700. Therebetween theelectrically insulated components, showerhead 300, plasma baffle insert500 and water box 400 are RF hot when activated upon by plasma generatorsystem 92 (FIG. 1E). Process chamber 50 also contains insulator ringliner 82, chamber liner 84 and other insulation liners to minimize orcompletely eliminate any line-of-sight between upper surface 62 and thevarious surfaces of chamber body assembly 90. The insulation liners helpminimize or eliminate plasma erosion of the metallic surfaces of chamberbody assembly 90. Therefore, substrate support 40 and a wafer containedthereon are a grounded path from RF powered showerhead 300 whilegenerating a plasma.

Referring to FIG. 1A, in one aspect, since process region 60 is isolatedfrom interior chamber region 59, a reactant gas or purge gas needs onlyadequately fill process region 60 to ensure sufficient exposure ofsubstrate 8 to the reactant gas or purge gas. In a conventional chemicalvapor deposition process, process chambers are required to provide acombined flow of reactants simultaneously and uniformly to the entiresubstrate surface in order to ensure that the co-reaction of thereactants occurs uniformly across the surface of substrate 8. During anALD process, process chamber 50 is used to sequentially expose substrate8 to chemical reactants, such as a gas or a plasma, that adsorb or reactas thin layers onto the surface of substrate 8. As a consequence, an ALDprocess does not require a flow of a reactant to simultaneously reachthe surface of substrate 8. Instead, a flow of a reactant needs to beprovided in an amount which is sufficient to adsorb a thin layer of thereactant on the surface of substrate 8 or in an amount which issufficient to react with an adsorbed layer on the surface of substrate8.

Since process region 60 may comprise a smaller volume when compared tothe inner volume of a conventional CVD chamber, a smaller amount of gasis required to fill process region 60 for a particular process in an ALDsequence. Since interior chamber region may have a volume of about 20 L,process region 60 is separated from interior chamber region 59 to have asmaller volume, such as about 3 L or less, preferably, about 2 L orless, and more preferably, about 1 L or less. In an embodiment for achamber adapted to process 200 mm diameter substrates, the volume ofprocess region 60 is about 1,000 cm³ or less, preferably, about 500 cm³or less, and more preferably, about 200 cm³ or less. In an embodimentfor a chamber adapted to process 300 mm diameter substrates, the volumeof process region 60 is about 3,000 cm³ or less, preferably, about 1,500cm³ or less, and more preferably, about 1,000 or less, such as about 800cm³ or less. In one example of a chamber adapted to process 300 mmdiameter substrates, process region 60 has a volume of about 770 cm³ orless. In another embodiment, substrate support 40 may be raised orlowered to adjust the volume of process region 60. For example,substrate support 40 may be raised to form process region 60 having avolume of about 770 cm³ or less. The smaller volume of process region 60requires less gas (e.g., process gas, carrier gas or purge gas) to beflowed into process chamber 50 during a process. Therefore, thethroughput of process chamber 50 is greater since less time is needed toprovide and remove gases and the operation cost is reduced since thewaste of chemical precursors and other gases may be minimized due to thesmaller amount of the gases.

FIG. 1B further illustrates an exploded view of lid assembly 100 andcomponents thereof. Lid support 103 having lower surface 102 and uppersurface 104 may be formed from a variety of materials including a metal.Preferably, lid support 103 is formed from a metal, such as aluminum,steel, stainless steel (e.g., iron-chromium alloys optionally containingnickel), iron, nickel, chromium, an alloy thereof or combinationsthereof. Lid assembly 100 may be attached to chamber body assembly 90 byhinges (not shown). Alignment slots 101 on lid support 103 arepositioned to be aligned with a post (not shown) attached to chamberbody assembly 90, once lid assembly is in a closed position. Lid support103 also contains support bracket 110 and handle assembly 107 mounted onupper surface 104. Handle assembly 107 may contain thermal isolator 108between handle 106 positioned on upper surface 104. Also, lid assembly100 has opening 120 with ledge surface 122 and wall surface 124.Multiple holes and openings, such as ports 116, 117 and 118, may alsopass through lid support 103 and may provide a passageway for conduit,tubing, hosing, fasteners, instruments and other devices. Lid support103 further contains holes that may not pass through. For example, holes119 may be threaded and used to receive a fastener, such as a screw or abolt.

Lid assembly 100 further contains isolation ring 200, showerhead 300,water box 400, plasma baffle insert 500, plasma screen insert 600,insulation cap 700 and gas manifold assembly 800. Each component (i.e.,isolation ring 200, showerhead 300, water box 400, plasma baffle insert500, plasma screen insert 600, insulation cap 700 or gas manifoldassembly 800) of lid assembly 100 may be scaled to process a substrateof varying size, such as a wafer with a 150 mm diameter, a 200 mmdiameter, a 300 mm diameter or larger. Also, each component may bepositioned and secured on lid support 103 by clips 780. Clip 780 latchesover upper surface 404 of water box 400 and is secured by a fastenerplaced through holes 119 (FIGS. 1A-1G). In one example, clip 780contains metal clip segment 784 disposed on insulator segment 782.Insulator segment 782 may be formed from an electrically insulatingmaterial, a thermally insulating material or a combination thereof.Insulator segments 782 provide electrical and thermal isolation betweenupper surface 404 and lid support 103 while clips 780 secure the variouscomponents of lid assembly 100. Axis 10 pass through the center of lidassembly 100 including, once aligned, opening 120 of lid support 103 andopening 220 of isolation ring 200, opening 320 of showerhead 300,opening 420 of water box 400, conical nose 520 of plasma baffle insert500, center portion 601 of plasma screen insert 600, channel 720 ofinsulation cap 700 and channel 820 of gas manifold assembly 800.

FIG. 1C depicts a view from underneath lid assembly 100, down axis 10,to illustrate upper surface 62 and lower surface 102 of lid support 103.Upper surface 62 of process region 60 is formed collectively of lowersurfaces 202 d and 205 d of isolation ring 200, lower surface 302 c ofshowerhead 300 and lower surface 502 of plasma baffle insert 500.Substrate 8 is positioned below upper surface 62 within process region60 and exposed to process gases during a deposition process. In oneembodiment, the substrate is sequentially exposed to at least twoprocess gases (e.g., gas or plasma) during an ALD process. In oneexample of an ALD process, substrate 8 is exposed to a first process gascoming from slots 510 of plasma baffle insert 500 and to a secondprocess gas coming from holes 310 of showerhead 300.

A view along axis 10 further illustrates that although opening 508 ofslot 510 is visible on lower surface 502, the other end of slot 510(e.g., opening 506 on upper surface 503, FIG. 5C) is not visible. Thisobscured view down axis 10 is due to the angle of slots 510 (angle α₁ inFIG. 5B) that depict a pathway between process region 60 and gas region640 above plasma baffle insert 500 does not have a line-of-sight. Theobscured pathway has many advantages over a non-obscured pathway havinga line-of-sight between process region 60 and gas region 640 including areduction or absence of a secondary plasma within or above plasma baffleinsert 500.

“Line-of-sight” as used herein refers to a straight path or asubstantially straight path between two points. The straight path or thesubstantially straight path may provide an unobstructed pathway or anunobscured pathway for a gas or a plasma to flow between at least twopoints. Generally, an obstructed pathway or an obscured pathwayprohibits or substantially reduces the passage of a plasma whilepermitting the passage of a gas. Therefore, a line-of-sight pathwayusually permits the passage of a gas or a plasma, while a pathway nothave a line of sight between two points prohibits or substantiallyreduces the passage of a plasma and permits the passage of a gas.

In one embodiment, a portion of upper surface 62, namely lower surface302 c and lower surface 502, may be roughened (e.g., machined) toproduce more surface area across upper surface 62. The increased surfacearea of upper surface 62 may increase adhesion of accumulated materialduring a deposition process, while decreasing contaminants due to theflaking of the accumulated material. In one example, the mean roughness(R_(a)) of each lower surface 302 c and lower surface 502 independentlymay be at least about 15 microinch (about 0.38 μm), preferably, about100 microinch (about 2.54 μm), and more preferably, about 200 microinch(about 5.08 μm) or higher. Lower surface 102 of lid support 103 may alsobe roughened to have a roughness of at least about 15 microinch (about0.38 μm), preferably, at least about 50 microinch (about 1.27 μm), forexample, about 54 microinch (about 1.37 μm).

FIGS. 1B and 1D further illustrates gas manifold assembly 800 containingconduit assembly 840, manifold cap assembly 850 and gas conduit assembly830. Manifold cap assembly 850 may have viewing window assembly 826 forobserving ignited plasma (FIG. 1A). Alternatively, manifold cap assembly850 may contain surface 825 which lacks a viewing window (FIG. 1D). Gasconduit assembly 830 may be connected to and in fluid communication withport 117 at flange 834 while extended to be connected to and in fluidcommunication with gas inlet 813 on manifold block 806 (FIGS. 1D and8D).

In one embodiment, plasma generator system 92 is attached to lidassembly 100 by RF strap 88 (FIG. 1D). A portion of plasma generatorsystem 92, namely RF stinger 94 and insulator 95 a, protrudes throughport 116 on lid support 103 and couples to showerhead 300 and water box400. Insulator 95 a maintains RF stinger 94 electrically isolated fromlid support 103 while RF strap electrically connects RF stinger 94 toregion 950 containing contacts 350 and 450 on showerhead 300 and waterbox 400. RF stinger 94 is a conductive material, such as a metal rod orelectrode, which may contain copper, brass, stainless steel, steel,aluminum, iron, nickel, chromium, alloys thereof, other conductivematerials or combinations thereof.

Plasma generator system 92 further contains plasma generator 97 that maybe mounted under chamber body 80 (FIG. 1E). Insulator 95 b may be placedbetween plasma generator 97 and chamber body 80 to electrically isolateplasma generator 97. Match 96 may protrude through insulator 95 b and bein electrical contact with chamber body 80. Plasma generator 97 furthercontains connector 98. In one example, connector 98 is an RF coaxialcable connector, such as a type N connector. Plasma generator system 92may be operated by plasma generator controller 22 connected to signalbus system 30. In one example, process conditions of plasma generatorsystem 92 may be set to have a chamber impendence of about 4 ohms withabout 9 amperes at about 300 watts. A plasma system and a processchamber that may be used in combination with lid assembly 100 or may beused as plasma generator system 92 and chamber body assembly 90 is theTXZ® CVD, chamber available from Applied Materials, Inc., located inSanta Clara, Calif. Further disclosure of plasma systems and processchambers is described in commonly assigned U.S. Pat. Nos. 5,846,332,6,079,356, and 6,106,625, which are incorporated herein by reference intheir entirety, to provide further disclosure for a plasma generator, aplasma chamber, a vapor deposition chamber, a substrate pedestal andchamber liners.

Chamber body assembly 90 of process chamber 50 contains insulator ringliner 82 that is used to reduce plasma exposure to chamber body 80 andhelps ensure that plasma is confined within process region 60 (FIG. 1F).Also, chamber body assembly 90 generally houses substrate support 40attached to post 42 within interior chamber region 59. Substrate support40 is movable in a vertical direction inside process chamber 50 usingsupport controller 20. In one embodiment, substrate support 40 isrotatable. Process region 60 is situated above substrate support 40 andbelow lid assembly 100, preferably, at least below showerhead 300,plasma baffle insert 500 and a portion of isolation ring 200.

Depending on the specific process, substrate 8 may be heated to somedesired temperature prior to or during a pretreatment step, a depositionstep, post-treatment step or other process step used during thefabrication process. For example, substrate support 40 may be heatedusing embedded heating element 45. Substrate support 40 may beresistively heated by applying an electric current from AC power supplyto heating element 45. Substrate 8 is, in turn, heated by substratesupport 40. Alternatively, substrate support 40 may be heated usingradiant heaters such as, for example, lamps (not shown).

Temperature sensor 46, such as a thermocouple, is also embedded insubstrate support 40 to monitor the temperature of substrate support 40in a conventional manner. The measured temperature is used in a feedbackloop to control AC power supply for heating element 45, such that thetemperature of substrate 8 may be maintained or controlled at a desiredtemperature which is suitable for the particular process application.Substrate lift pins (not shown) may also be embedded in substratesupport 40 and are used to raise substrate 8 from support surface 41.

Vacuum pumping system 36 is used to evacuate and to maintain thepressure inside process chamber 50 (FIG. 1F). Vacuum pumping system 36may be connected to process chamber 50 by pumping port 38 and valve 37.Gas manifold assembly 800, through which process gases are introducedinto process chamber 50, is located above substrate support 40. Gasmanifold assembly 800 may be connected to a gas panel, which controlsand supplies various process gases to process chamber 50.

Gas sources 70 a, 70 b, 70 c, 70 d, and 70 e provide precursor gas,carrier gas or purge gas to process chamber 50 through conduit system34. Gas sources 70 a, 70 b, 70 c, 70 d and 70 e may be directly orindirectly connected to a chemical supply or a gas supply. The chemicalor gas supplies include a tank, an ampoule, a bubbler, a vaporizer oranother container used to store, transfer or form a chemical precursor.The chemical or gas supply may also be from an in-house source. Propercontrol and regulation of the gas flows from gas sources 70 a, 70 b, 70c, 70 d, and 70 e to gas manifold assembly 800 are performed by valveassemblies 72 a, 72 b, 72 c, 72 d and 72 e coupled to control unit 51.Gas manifold assembly 800 allows process gases to be introduced intoprocess chamber 50 and may optionally be heated to prevent condensationof any gases within the conduits or lines of gas manifold assembly 800.

Each valve assembly 72 a, 72 b, 72 c, 72 d and 72 e may comprise adiaphragm and a valve seat. The diaphragm may be biased open or closedand may be actuated closed or open respectively. The diaphragms may bepneumatically actuated or may be electrically actuated. Examples ofpneumatically actuated valves are available from Fujikin and Veriflowand examples of electrically actuated valves are available from Fujikin.Control unit 51 may be coupled to valve assemblies 72 a, 72 b, 72 c, 72d and 72 e to control actuation of the diaphragms of the valves.Pneumatically actuated valves may provide pulses of gases in timeperiods as low as about 0.020 seconds. Electrically actuated valves mayprovide pulses of gases in time periods as low as about 0.005 seconds.Generally pneumatically and electrically actuated valves may providepulses of gases in time periods as high as about 3 seconds. Althoughhigher time period for gas pulsing is possible, a typical ALD processutilizes ALD valves to generate pulses of gas while being opened for aninterval of about 5 seconds or less, preferably about 3 seconds or less,and more preferably about 2 seconds or less. In one embodiment, an ALDvalve pulses for an interval in a range from about 0.005 seconds toabout 3 seconds, preferably from about 0.02 seconds to about 2 secondsand more preferably from about 0.05 seconds to about 1 second. Anelectrically actuated valve typically requires the use of a drivercoupled between the valve and control unit 51. In another embodiment,each valve assemblies 72 a, 72 b, 72 c, 72 d and 72 e may contain a massflow controller (MFC) to control gas dispersion, gas flow rates andother attributes to an ALD pulse sequence.

A precursor or a gas delivery system within an ALD apparatus is used tostore and dispense chemical precursors, carrier gases, purge gases orcombinations thereof. The delivery system may contain valves (e.g., ALDvalves or MFCs), conduits, reservoirs, ampoules and bubblers, heaterand/or control unit systems, which may be used with process chamber 50or lid assembly 100 and coupled in fluid communication with gas manifold800 or conduit system 34. In one example, a delivery system may containgas sources 70 a-70 e and valve assemblies 72 a, 72 b, 72 c, 72 d, and72 e coupled to control unit 51. Delivery systems configured for an ALDprocess system are described in commonly assigned and co-pending U.S.Ser. No. 11/127,753, entitled “Apparatus and Methods for Atomic LayerDeposition of Hafnium-Containing High-k Materials,” filed May 12, 2005,and published as US 2005-0271812, U.S. Ser. No. 11/119,388, entitled“Control of Gas Flow and Delivery to Suppress the Formation of Particlein an MOCVD/ALD System,” filed Apr. 29, 2005, and published as US2005-0252449, U.S. Ser. No. 10/281,079, entitled “Gas Delivery Apparatusfor Atomic Layer Deposition,” filed Oct. 25, 2002 and published as US2003-0121608, and U.S. Ser. No. 10/700,328, entitled “Precursor DeliverySystem with Rate Control,” filed Nov. 3, 2003 and published as US2005-009859, which are incorporated herein by reference in theirentirety.

Control unit 51, such as a programmed personal computer, work stationcomputer, or the like, may be coupled to process chamber 50 to controlprocessing conditions. For example, control unit 51 may be configured tocontrol flow of various process gases and purge gases from gas sources70 a-70 e through valve assemblies 72 a-72 e during different stages ofa substrate process sequence. Illustratively, control unit 51 comprisescentral processing unit (CPU) 52, support circuitry 54, and memory 56containing associated control software 58.

Software routines, as required, may be stored in memory 56 or executedby a remotely located source (e.g., computer or server). The softwareroutines are executed to initiate process recipes or sequences. Thesoftware routines, when executed, transform the general purpose computerinto a specific process computer that controls the chamber operationduring a chamber process. For example, software routines may be used toprecisely control the activation of gas sources 70 a-70 e through valveassemblies 72 a-72 e during the execution of process sequences accordingto the embodiments described herein. Alternatively, the softwareroutines may be performed in the hardware, as an application specificintegrated circuit or other type of hardware implementation or acombination of software or hardware.

Control unit 51 may be one of any form of general purpose computerprocessor that can be used in an industrial setting for controllingvarious chambers and sub-processors. CPU 52 may use any suitable memory56, such as random access memory, read only memory, floppy disk drive,compact disc drive, hard disk or any other form of digital storage,local or remote. Various support circuits may be coupled to the CPU 52for supporting process chamber 50. Control unit 51 may be coupled toanother controller that is located adjacent individual chambercomponents, such as programmable logic controllers of valve assemblies72 a-72 e. Bi-directional communications between control unit 51 andvarious other components of process chamber 50 are handled throughnumerous signal cables collectively referred to as signal buses 30, someof which are illustrated in FIG. 1F. In addition to control of processgases and purge gases from gas sources 70 a-70 e, valve assemblies 72a-72 e and any programmable logic controllers, control unit 51 may beconfigured to be responsible for automated control of other activitiesused during a fabrication process. Control unit 51 is connected toplasma generator controller 22, vacuum pumping system 36 and supportcontroller, including temperature monitoring and control and control oflift pins (not shown).

Isolation ring 200 contains opening 220 (FIGS. 2A-2B) and may bepositioned between showerhead 300 and lid support 103 (FIGS. 1A-1B).Isolation ring 200 contains upper surface 204 to support showerhead 300.Opening 220 may be aligned with opening 120 such that axis 10 passesthrough each center. Isolation ring contains inner surfaces 205 a, 205b, 205 c and 205 d that taper inward towards axis 10.

Isolation ring 200 further contains lower surfaces 202 a, 202 b, 202 cand 202 d. Lower surface 202 a may be used to contact ledge surface 122of lid support 103 while supporting isolation ring 200. Lower surfaces202 d and 205 d forms process region 60 while contributing to uppersurface 62 therein (FIG. 1C). The portion of upper surface 62contributed by lower surface 202 d forms an outer ring seal betweenprocess region 60 and interior chamber region 59. Isolation ring 200 maybe formed from an electrically insulating material that is plasmaresistant or chemical resistant against the process reagents. Isolationring 200 may also contain a thermally insulating material. Materialsuseful to construct isolation ring 200 include ceramic, quartz, fusedquartz, sapphire, pyrolytic boron nitrite (PBN) material, glass,plastic, derivatives thereof, or combinations thereof.

Showerhead 300 contains opening 320 (FIGS. 3A-3B) and may be positionedbetween isolation ring 200 and water box 400 (FIG. 1A-1B). Showerhead300 contains upper surfaces 303, 304, and 306, where upper surfaces 304and 306 may be used to support water box 400. Wall surfaces 305 a and305 b are disposed between upper surfaces 303, 304 and 306. Showerhead300 further contains lower surfaces 302 a, 302 b, and 302 c. Lowersurface 302 a may be used to contact upper surface 204 of isolation ring200 while supporting showerhead 300. Lower surface 302 c also formsprocess region 60 while contributing to upper surface 62 therein (FIG.1C). Showerhead 300 may be formed from a variety of materials includinga metal or another electrically conductive material. Preferably,showerhead 300 is formed from a metal, such as aluminum, steel,stainless steel, iron, nickel, chromium, an alloy thereof orcombinations thereof.

Opening 320 passes through showerhead 300 and may be aligned withopenings 120 and 220 such that axis 10 passes through each center (FIG.1B). Also, opening 320 passes through ring assembly 330. Ring assembly330 is positioned in the center of showerhead 300 and may be used tohouse plasma baffle insert 500. Ring assembly 330 contains ring 328disposed above the surface of upper surface 303. Ledge 332 protrudesinwardly from ring 328 towards axis 10 and is used to support plasmabaffle insert 500 thereon. Ledge 322 protrudes outwardly from ring 328away from axis 10 and is used to support water box 400 in conjunctionwith upper surfaces 304 and 306. Upper surface 324 of ring 328 is usedto support plasma screen insert 600.

Upper surface 303 of showerhead 300 receives a process gas fordistributing into process region 60 through holes 310. Holes 310 passthrough showerhead 300 from upper surface 303 to lower surface 302 c andprovide fluid communication therethrough. Holes 310 in showerhead 300may have a diameter within a range from about 0.10 mm to about 1.00 mm,preferably, from about 0.20 mm to about 0.80 mm, and more preferably,from about 0.40 mm to about 0.60 mm. Showerhead 300 may have at leastabout 100 holes, preferably, about 1,000 holes, and more preferably,about 1,500 holes or more. Showerhead 300 may have as many as 6,000holes or 10,000 holes depending on size of the holes 310, thedistribution pattern of the holes 310, size of substrate and desiredexposure rate. Holes 310 may have a varying or consistent geometry fromhole to hole. In one example, showerhead 300 is constructed from metal(e.g., aluminum or stainless steel) and has 1,500 holes that are formedwith a diameter of 0.50 mm.

Showerhead 300 contains opening 320 (FIG. 3) and may be positionedbetween isolation ring 200 and water box 400 (FIG. 1A-1B). Showerhead300 contains upper surfaces 303, 304 and 306, where upper surfaces 304and 306 may be used to support water box 400. Wall surfaces 305 a and305 b are disposed between upper surfaces 303, 304 and 306. Showerhead300 further contains lower surfaces 302 a, 302 b and 302 c. Lowersurface 302 a may be used to contact upper surface 204 of isolation ring200 while supporting showerhead 300. Lower surface 302 c also formsprocess region 60 while contributing upper surface 62 therein (FIG. 1C).Showerhead 300 may be formed from a variety of materials including ametal or another electrically conductive material. Preferably,showerhead 300 is formed from a metal, such as aluminum, steel,stainless steel, iron, nickel, chromium, alloys thereof or combinationsthereof.

A plurality of holes 310 are formed through showerhead 300, so thatupper surface 303 is in fluid communication to lower surface 302 c.Holes 310 may have a variety of sizes and be contained across uppersurface 303 and lower surface 302 c in multiple patterns. Each hole ofthe plurality of holes 310 may have a diameter within a range from about0.10 mm to about 1.00 mm, preferably, from about 0.20 mm to about 0.80mm, and more preferably, from about 0.40 mm to about 0.60 mm, such asabout 0.51 mm (0.020 in). Showerhead 300 has at least about 100 holes,preferably, about 1,000 holes, and more preferably, about 1,500 holes ormore. For example, showerhead 300 may have as many as 6,000 holes or10,000 holes depending on size of holes 310, the pattern of the holes,size of substrate and desired exposure rate. Preferably, showerhead 300is constructed from a metal (e.g., aluminum or stainless steel) and has1,500 holes that are formed with a diameter of about 0.50 mm.

Water box 400, containing opening 420 (FIGS. 4A-4B), may be positionedon top of showerhead 300 and used to regulate the temperature byremoving heat from lid assembly 100 (FIG. 1A-1B). Opening 420 containsledge surfaces 414 a and 414 b and inner surfaces 416 a, 416 b and 416c. A plurality of passageways 440 radial extend from inner surface 416 binwardly through water box 400 to lower surface 402 c. Opening 420 isadapted to receive plasma baffle insert 500, plasma screen insert 600,insulation cap 700. Insulation cap 700 may be positioned on ledgesurface 414 a. Water box 400 may be formed from a variety of materialsincluding a metal. Preferably, water box 400 is formed from aluminum,steel, stainless steel, iron, nickel, chromium, an alloy thereof,another metal, or combinations thereof. Lower surfaces 402 a and 402 bof water box 400 rests on upper surfaces 304 and 306 of showerhead 300.Water box 400 also contains upper surface 403 surrounded by innersurface 405 which has upper surface 404. Water box 400 helps remove heatfrom lid assembly 100, especially from showerhead 300. Upper surface 403contains inlet 410 and outlet 412 that are in fluid communication withpassageway 430. During a deposition process, a fluid at an initialtemperature is administered into water box 400 through inlet 410. Thefluid absorbs heat while traveling along passageway 430. The fluid at ahigher temperature is removed from water box 400 through outlet 412.

The fluid may be in liquid, gas or supercritical state and is capable ofadsorbing and dissipating heat in a timely manner. Liquids that may beused in water box 400 include water, oil, alcohols, glycols, glycolethers, other organic solvents, supercritical fluids (e.g., CO₂)derivatives thereof or mixtures thereof. Gases may include nitrogen,argon, air, hydrofluorocarbons (HFCs), or combinations thereof.Preferably, water box 400 is supplied with water or a water/alcoholmixture.

Inlet 410 may be adapted to receive nozzle 411 connected to line 425(e.g., hose) in fluid communication with a fluid source. Similarly,outlet 412 may be adapted to receive nozzle 413 connected to line 427 influid communication with a fluid return. The fluid source and fluidreturn may be an in-house cooling system or an independent coolingsystem. Lines 425 and 427 are connected to source nozzle 421 and returnnozzle 423 held in positioned on lid support 103 by support bracket 110.Lines 425 and 427 may be a tube, a hose, a conduit or a line.

In one embodiment, the fluid may be administered into water box 400 at atemperature within a range from about −20° C. to about 40° C.,preferably, from about 0° C. to about 20° C. The temperature, flow rate,and fluid composition may be adjusted accordingly to remove theappropriate amount of heat from lid assembly 100 including showerhead300 while maintaining water box 400 at a predetermined temperature.Water box 400 may be maintained at a predetermined temperature within arange from about 0° C. to about 100° C., preferably, from about 18° C.to about 65° C., and more preferably, from about 20° C. to about 50° C.

In an alternative embodiment, FIGS. 4C-4F illustrate passageways 430 c,430 d, 430 e and 430 f to provide several different geometries that maybe used to replace passageway 430. Passageways 430 c-430 f may include apartial loop 432 c (FIG. 4C), a single loop 432 d (FIG. 4D), multipleloops 432 e (FIG. 4E) or contain branches or spurs 432 f around opening420 (FIG. 4F).

Gas region 540 is above upper surface 303 of showerhead 300 and belowthe lower surface 402 c of water box 400. Passageways 440 extend frominner surface 416 b, pass through water box 400 and into gas region 540.Inner surface 416 b may be inwardly concaved such to form gas region 441that is situated between inner surface 416 b and plasma screen insert600 and insulation cap 700 (FIG. 7C). Gas region 441 encompasses plasmascreen insert 600 to maintain fluid communication with slots 614.Passageways 440 provide fluid communication between gas regions 441 and540. Water box 400 contains numerous passageways 440. For example, waterbox 400 may contain at least about 10 passageways, preferably, at leastabout 24 passageways, and more preferably, at least about 36 passagewaysor more.

FIGS. 5A-5F illustrate schematic views of plasma baffle insert 500 thatmay be included as a portion of lid assembly 100 as described in severalembodiments. Plasma baffle insert 500 is configured to receive a processgas from gas region 640 and distribute or inject the process gas intoprocess region 60. Preferably, plasma baffle insert 500 is configured todistribute the process gas at a predetermined angle. Upper surface 503contains slots 510 extending through plasma baffle insert 500 to lowersurface 502 for distributing the process gas into process region 60.

Plasma baffle insert 500 is illustrated containing conical nose 520extending from upper surface 503 to nose surface 522 (FIG. 5A). Nosesurface 522 may have a variety of geometries, such as flat (FIG. 5B) orconical nose 520 may extend to a point (not illustrated). Preferably,nose surface 522 is substantially, horizontally flat for contactingplasma screen insert 600. Conical nose 520 may extend into gas region640, which is a region formed above plasma baffle insert 500, belowplasma screen insert 600 and within ring assembly 330. Conical nose 520occupies a predetermined volume within gas region 640. A less amount ofprocess gas is required to fill gas region 640 during a depositionprocess if conical nose 520 occupies a larger volume. Therefore, aquicker ALD cycle is realized since a reduced amount of process gas ismore quickly administered and removed from gas region 640 during eachhalf cycle of an ALD process.

Plasma baffle insert 500 contains lower rim 512 having lower surface 502and upper rim 514 having upper surface 505 and lower surface 504. Lowerrim 512 and upper rim 514 are separated by gap 513. A gasket may beplaced within gap 513 to provide more conductivity or a better seal. Agasket may include an o-ring or sealant. Preferably, the gasket is a RFgasket and contains a conductive material, such as a metal cable or aconductively doped-polymeric material. In a preferred example, a RFgasket, such as a twisted stainless steel cable, is placed along gap 513to provide a more conductive contact with showerhead 300. Plasma baffleinsert 500 may be positioned within opening 320 of showerhead 300 sothat lower surface 504 of upper rim 514 rests on ledge 332 of showerhead300 (FIG. 1A-1B). Plasma baffle insert 500 is also circumferentiallysurrounded by ring assembly 330 within opening 320. Plasma baffle insert500 may be formed from aluminum, steel, stainless steel, iron, nickel,chromium, other metals, alloys thereof or combinations thereof.

Plasma baffle insert 500 contains a plurality of slots 510, such thatopenings 508 of upper surface 503 is in fluid communication to openings506 of lower surface 502 (FIGS. 5B and 5C). Slots 510 provide access fora process gas to flow from gas region 640 and into process region 60 ata predetermined angle. Ideally, slots 510 direct the process gas tocontact substrate 8 or support surface 41 at an injection angle α₁measured between axis 10 and line 532. Axis 10 extends perpendicularthrough lower surface 502 while line 532 extends along the plane ofslots 510. Therefore, slots 510 contained within plasma baffle insert500 are positioned at injection angle α₁ to direct a process gas havinga flow pattern at injection angle α₁, as depicted in FIGS. 5C and 9C-9D.

In some embodiments, plasma baffle insert 500 may contain trough 501 ora plurality of holes 530 to assist in moving process gases from uppersurface 503. In one embodiment, plasma baffle insert 500 may containtrough 501 around an outside perimeter of slots 510, as depicted inFIGS. 5A-5C. Alternatively, slots 510 may extend into trough 501 (notshown).

In another embodiment, plasma baffle insert 500 may contain holes 530around an outside perimeter of conical nose 520, as depicted in FIGS.5D-5F. Each hole 530 extends from upper surface 503 to lower surface 502along axial line 538. In one example, each hole 530 has a constantdiameter along axis line 538. Preferably, each hole 530 contains upperpassageway 526 a and lower passageway 526 b separated by choke 528. Thediameter of upper passageway 526 a is usually larger than the diameterof lower passageway 526 b.

In some embodiments, a process gas with a flow pattern parallel orperpendicular to support surface 41 (i.e., about 0° or about 90° frominjection angle α₁) may unevenly accumulate a chemical precursor acrossthe surface of substrate 8. During a vapor deposition process, substrate8 may exposed to the process gas at a predetermined angle of less thanabout 90°, but more than about 0°, to ensure an even exposure of theprocess gas. In one embodiment, injection angle α₁ of slots 510 may beat an angle within a range from about 20° to about 70°, preferably, fromabout 30° to about 60°, and more preferably, from about 40° to about50°, such as about 45°. The process gas may have a circular pathwayinherited from the injection angle α₁ of slots 510. The circular pathwayusually has a vortex geometry, a helix geometry, a spiral geometry, aswirl geometry, a twirl geometry, a twist geometry, a coil geometry, acorkscrew geometry, a curl geometry, a whirlpool geometry, orderivatives thereof.

Holes 530 contained within plasma baffle insert 500 may be positioned atinjection angle α₅ to direct a process gas having flow pattern 912 atinjection angle α₅, as depicted in FIGS. 5F and 9C-9D. In anotherembodiment, injection angle α₅ of holes 530 may be at an angle within arange from about 0° to about 60°, preferably, from about 15° to about50°, and more preferably, from about 30° to about 40°, such as about35°. Flow pattern 912 of the process gas may have a conical pathwayinherited from the injection angle α₅ of holes 530.

A secondary plasma or back diffusion of gasses within or above theplasma baffle insert 500 may be avoided by limiting the width and lengthof slots 510 and holes 530. Also, a secondary plasma within or above theplasma baffle insert 500 may be avoided or limited by positioning slots510 at a predetermined injection angle α₁, such that there is not aline-of-sight through plasma baffle insert 500, along axis 10, fromsupport surface 41 to gas region 640 (FIG. 1C). The secondary plasmawithin or above the plasma baffle insert 500 may also be avoided orlimited by positioning holes 530 at a predetermined injection angle α₅,such that there is not a line-of-sight through plasma baffle insert 500,along axial line 538, from support surface 41 to gas region 640 (FIG.1F).

Therefore, the lack of a line-of-sight forms an obscured pathway downeach slot 510 or hole 530. For example, slots 510 may have a widthwithin a range from about 0.50 mm to about 1.00 mm, preferably, fromabout 0.60 mm to about 0.90 mm, and more preferably, from about 0.70 mmto about 0.80 mm, such as about 0.76 mm (0.030 in). Also, slots 510 mayhave a length within a range from about 3 mm to about 60 mm, preferably,from about 10 mm to about 50 mm, and more preferably, from about 20 mmto about 30 mm, such as about 21.6 mm (0.850 in). Plasma baffle insert500 may have at least about 10 slots, preferably, about 15 slots, andmore preferably, about 20 slots or more. In one example, plasma baffleinsert 500 is constructed from metal (e.g., aluminum or stainless steel)and has 20 slots that are about 0.76 mm wide and about 2.16 mm long.

In one embodiment, each hole 530 may have a diameter within a range fromabout 0.13 mm (0.005 in) to about 2.54 mm (0.100 in), preferably, fromabout 0.26 mm (0.010 in) to about 2.29 mm (0.090 in), and morepreferably, from about 0.51 mm (0.020 in) to about 1.90 mm (0.075 in).In one example, each hole 530 may contain upper passageway 526 a havinga diameter within a range from about 1.27 mm (0.050 in) to about 2.29 mm(0.090 in), preferably, from about 1.52 mm (0.060 in) to about 2.03 mm(0.080 in), such as about 1.78 mm (0.070 in). Also, each hole 530 maycontain lower passageway 526 b having a diameter within a range fromabout 0.38 mm (0.015 in) to about 1.27 mm (0.050 in), preferably, fromabout 0.64 mm (0.025 in) to about 1.02 mm (0.040 in), such as about 0.81mm (0.032 in). In one example, each hole 530 contains upper passageway526 a having a diameter within a range from about 1.5 mm to about 2 mmand lower passageway 526 b having a diameter within a range from about0.6 mm to about 1 mm. Plasma baffle insert 500 may have no holes or aplurality of holes 530, such as about 4 holes, preferably, about 8holes, and more preferably, about 16 holes or more. In one example,plasma baffle insert 500 is constructed from metal (e.g., aluminum orstainless steel) and has 8 holes.

In another embodiment, upper surface 503 of plasma baffle insert 500 issloped from conical nose 520 towards upper rim 514. In a preferredexample, the process gas is directed from holes 612 towards conical nose520 and down upper surface 503 towards upper rim 514. In one embodiment,plasma baffle insert 500 is formed with upper surface 503 slopeddownwardly from conical nose 520 to provide greater mechanical strengthand to control varying conductance and flow rates during a process.Upper surface 503 may have a slope with an angle α₂ measured betweenlines 535 and 537. Line 535 extends along the plane of upper surface 503and line 537 is perpendicular or substantially perpendicular to axis 10(FIG. 5B). Upper surface 503 is configured to receive a process gasalong various portions of openings 506 relative to angle α₂. Therefore,angle α₂ may be at a predetermined angle in order to eject the processgas from openings 508 of slots 510 with a consistent flow rate along thelength of openings 506. In one embodiment, upper surface 503 may besloped at an angle α₂ within a range from about 0° to about 45°,preferably, from about 5° to about 30°, and more preferably, from about10° to about 200, such as about 150. In another embodiment, uppersurface 503 may be sloped at an angle α₂ within a range from about 0° toabout 45°, preferably, from about 2° to about 20°, and more preferably,from about 3° to about 10°, such as about 5°.

Slots 510 disposed around conical nose 520 pass through plasma baffleinsert 500 between opening 506 on upper surface 503 (FIG. 5C) andopening 508 on lower surface 504 (FIG. 1C). Openings 506 and 508 may bedisposed around conical nose 520 at angle α₃, measured between line 531and radial line 533. Line 531 extends along the length of opening 506and radial line 533 extends perpendicular from axis 10. Line 531 mayalso extend along the length of opening 508 (not shown). In oneembodiment, openings 506 and 508 may be disposed around conical nose 520and are tangential or substantially tangential to dashed circle 539 atangle α₃. Therefore, line 531, extending along the length of opening506, may intersect a point on dashed circle 539 and is tangent orsubstantially tangent to dashed circle 539 at angle α₃. Dashed circle539 may have a radius of a length within a range from about 0.5 mm toabout 5 mm, preferably, from about 1 mm to about 3 mm, and morepreferably, from about 1.5 mm to about 2.5 mm, for example, about 2 mm(about 0.081 inch). In other embodiments, openings 506 and 508 may beradially disposed around or tangentially about conical nose 520. Also,openings 506 and 508 may have an angle α₃ at an angle within a rangefrom about 0° to about 90°, preferably, from about 20° to about 45°, andmore preferably, from about 30° to about 40°, such as about 35°.

In one embodiment, plasma screen insert 600 and insulation cap 700 maybe placed between gas manifold assembly 800 and plasma baffle insert 500to prohibit or to limit plasma generation therebetween (FIGS. 1A-1B).Plasma screen insert 600 and insulation cap 700 may also prohibit orlimit the transfer of heat from plasma baffle insert 500 to gas manifoldassembly 800. Plasma screen insert 600 and insulation cap 700independently each contain an electrically insulating material, such asceramic, quartz, glass, sapphire or a derivative thereof.

Plasma screen insert 600 contains inner region 630 and outer region 632separated by ring assembly 631 (FIGS. 6A-6B). Ring assembly 631 containswall surface 626, inner wall surfaces 605 a and 605 b and upper surfaces604 and 606. Inner region 630 is bound within inner wall surfaces 605 aand 605 b. Inner region 630 contains center portion 601 encompassed by aplurality of holes 612 that pass through plasma screen insert 600. Aprocess gas within inner region 630 is exposed to upper surface 602 andis in fluid communication through holes 612 to lower surface 603 and gasregion 640. Center portion 601 generally has no holes between uppersurface 602 and lower surface 603.

Outer region 632 extends from ring assembly 631 and contains a pluralityof slots 614 that radially extend along upper surface 608. Slots 614direct a secondary process gas from outer region 632 to gas region 540.Axis 10 extends through the center of plasma screen insert 600 such thatthe plurality of holes 612 extend parallel or substantially parallel toaxis 10 and the plurality of slots extend perpendicular or substantiallyperpendicular to axis 10.

FIG. 1A illustrates plasma screen insert 600 positioned on ring assembly330 of showerhead 300 and on conical nose 520 of plasma baffle insert500. Nose surface 522 is in contact to center portion 601 of lowersurface 603. During a deposition process, a secondary plasma aboveplasma screen insert 600 within the gas region 640 may be avoided bylimiting the width and length of slots 614 and the diameter of holes612. For example, slots 614 may have a width within a range within arange from about 0.10 mm to about 1.00 mm, preferably, from about 0.20mm to about 0.80 mm, and more preferably, from about 0.40 mm to about0.60 mm, such as about 0.50 mm. Plasma screen insert 600 may have atleast about 10 slots, preferably, about 20 slots, and more preferably,about 36 slots or more. In one embodiment, plasma screen insert 600 hasthe same amount of slots 614 as water box 400 has passageways 440.

Plasma screen insert 600 contains holes 612 that may have a diameterwithin a range from about 0.5 mm to about 5 mm, preferably, from about 1mm to about 3 mm, and more preferably, from about 1.2 mm to about 1.8mm, such as about 1.50 mm (0.060 in). Plasma screen insert 600 containsa plurality of holes 612 may have about 50 holes or more, preferably, atleast about 100 holes, and more preferably, about 150 holes or more, forexample. In one example, plasma screen insert 600 is constructed ofceramic and has 36 slots that are about 0.51 mm (0.020 in) wide andabout 156 holes that have a diameter of about 1.52 mm. Preferably,plasma screen insert 600 has a circular geometry, but may have adifferent geometry in alternative embodiments (e.g., oval geometry).Plasma screen insert 600 may have a diameter within a range from about 1inch (about 2.54 cm) to about 12 inches (about 30.52 cm), preferably,from about 2 inches (about 5.08 cm) to about 8 inches (about 20.36 cm),and more preferably, from about 3 inches (about 7.62 cm) to about 4inches (about 10.16 cm). Plasma screen insert 600 may have a thicknessof about 1 inch (about 2.54 cm) or less, preferably, about 0.5 inches(about 1.27 cm) or less, and more preferably, about 0.25 inches (about0.64 cm), such as about 0.125 inches (about 0.32 cm), where thethickness is measured along a plane parallel to axis 10 passing throughplasma screen insert 600. In one example of plasma screen insert 600,inner region 630 has a thickness of about 0.125 inches (about 0.32 cm)or less and ring assembly 631 has a thickness of about 0.25 inches(about 0.64 cm) or less.

Insulation cap 700 has upper surface 704 and lower surfaces 703 a, 703b, 703 c, 703 d and 703 e (FIGS. 7A-7C). Insulation cap 700 contains atleast one channel extending from upper surface 704 to lower surfaces 703a-703 e. In one example, insulation cap 700 contains only one channel,and a conduit outside of insulation cap 700 may be used to direct asecond process gas. In another example, insulation cap 700 containsmultiple channels, such as three channels, four channels or more (notshown). In a preferred example, insulation cap 700 contains at least twochannels, such as channels 710 and 720. Channel 720 extends from uppersurface 704, through insulation cap 700, to form expanding channel 722.Expanding channel 722 tapers from channel 720 at upper portion 721 tolower portion 723 and contains lower surface 703 e (FIG. 7B). Axis 10may pass through the center of channel 720 and expanding channel 722(FIG. 7C). Channel 710 extends from upper surface 704, throughinsulation cap 700, to groove 725. In one embodiment, channel 710 has asmaller radius than channel 710. Groove 725 contains lower surface 703 cand is formed encircling the bottom of insulation cap 700 (FIG. 7B).Upper surface 704 also contains holes 707 which are configured forreceiving fasteners (e.g., bolts or screws) to secure gas manifoldassembly 800 thereon.

Insulation cap 700 may be positioned on water box 400 such that lowersurface 703 a contacts and is supported by water box 400. Lower surfaces703 b, 703 c, 703 d and 703 e either contact plasma screen insert 600 orform regions therebetween (FIG. 7C). Lower surface 703 d is placed intocontact with upper surface 602 of plasma screen insert 600 to form gasregion 744. Gas regions 742 and 744 and gap 726 are each formed betweeninsulation cap 700 and plasma screen insert 600.

Gas region 742 is formed between groove 725 containing lower surface 703c and a portion of outer region 632 of plasma screen insert 600,including trough 622 and wall surfaces 624 and 626 (FIG. 7C). Gas region742 extends around and above outer region 632 to encompass gas region744. Channel 710 is in fluid communication with gas region 742 throughlower surface 703 c. Also, gas region 540 is in fluid communication withgas region 742, since slots 614 extend from wall surface 624 topassageways 440, which further extend through water box 400 and into gasregion 540. Slots 614 in combinations with lower surface 703 b ofinsulation cap 700 forms these passageways. During a deposition process,a process gas flows down channel 710, enters gas region 742, flows alongtrough 622 and exits through slots 614. Gap 726 generally contains ano-ring after assembling the components.

Gas region 744 is formed in part by lower surface 703 e of insulationcap 700 and a portion of inner region 630 of plasma screen insert 600,including upper surface 602 and center portion 601. Channel 720 is influid communication with gas region 744 through lower surface 703 e.Channel 720 is perpendicularly in-line with center portion 601 (alongaxis 10) which does not contain holes 612. In a preferred example, thediameter of channel 720 is smaller than the diameter of center portion601 to help deflect a process gas. Expanding channel 722 expands fromupper portion 721 to lower portion 723 and covers most of inner region630 and upper surface 602 within gas region 744. Also, gas region 640 isin fluid communication with gas region 744, since holes 612 extend fromthrough plasma screen insert 600.

During a deposition process, a process gas flows down channel 720,enters gas region 744 and exits through holes 612. Center portion 601deflects any process gas having a flow path perpendicular to uppersurface 602 coming straight from channel 720. Therefore, the obscuredflow path reduces or eliminates a secondary plasma from forming betweenplasma baffle insert 500 and gas manifold assembly 800.

Expanding channel 722 has an inner diameter which increases from upperportion 721 to lower portion 723 (FIG. 7B). In one embodiment, the innerdiameter of expanding channel 722 for a chamber adapted to process a 300mm diameter substrate is within a range from about 0.5 cm to about 7 cm,preferably, from about 0.8 cm to about 4 cm, and more preferably, fromabout 1 cm to about 2.5 cm at upper portion 721 of expanding channel 722and within a range from about 2 cm to about 15 cm, preferably, fromabout 3.5 cm to about 10 cm, and more preferably, from about 4 cm toabout 7 cm at lower portion 723 of expanding channel 722. In general,the above dimension apply to an expanding channel adapted to provide atotal gas flow rate within a range from about 100 sccm to about 10,000sccm.

In other specific embodiments, the dimension of expanding channel 722may be altered to accommodate a certain gas flow therethrough. Ingeneral, a larger gas flow will require a larger diameter for expandingchannel 722. In one embodiment, expanding channel 722 may be shaped as atruncated cone (including shapes resembling a truncated cone). Whether aprocess gas is provided toward the walls of expanding channel 722 ordirectly downward towards substrate 8, the velocity of the gas flowdecreases as the process gas travels through expanding channel 722 dueto the expansion of the process gas. The reduction of the process gasvelocity helps reduce the likelihood the gas flow will blow offreactants absorbed on the surface of substrate 8.

The diameter of expanding channel 722 gradually increases from upperportion 721 to lower portion 723. The gradual increase of the diametermay allow less of an adiabatic expansion of a process gas throughexpanding channel 722 which helps to control the process gastemperature. For instance, a sudden adiabatic expansion of a gasdelivered through gas conduits 882 and 884 into channels 820 and 720 mayresult in a drop of the gas temperature which may cause condensation ofa precursor vapor and formation of particles. On the other hand, agradually expanding channel 722 according to some embodiments isbelieved to provide less of an adiabatic expansion of a process gas.Therefore, more heat may be transferred to or from the process gas, and,thus, the gas temperature may be more easily controlled by controllingthe surrounding temperature (i.e., controlling the temperature by waterbox 400). Expanding channel 722 may comprise one or more tapered innersurfaces, such as a tapered straight surface, a concave surface, aconvex surface, a combination thereof or may comprise sections of one ormore tapered inner surfaces (i.e., a portion tapered and a portionnon-tapered).

Gap 726 is also formed between insulation cap 700 and plasma screeninsert 600. Gap 726 is formed since a portion of lower surface 703 cwithin groove 725 does not contact upper surfaces 604 and 606 and innerwall surface 605 a of ring assembly 631 contained on plasma screeninsert 600. An o-ring may be positioned within gap 726 while placinginsulation cap 700 onto plasma screen insert 600.

Gas manifold assembly 800 includes conduit assembly 840 and manifold capassembly 850 containing gas conduit assembly 830 (FIGS. 8A-8B). Conduitassembly 840 contains gas conduits 836 and 838 within upper manifold 844and lower manifold 842. Gas manifold assembly 800 may be attached to lidassembly 100 by a fastener (e.g., bolt or screw) placed through holes843. In one embodiment, conduits 836 and 838, independently, are influid communication with conduit system 34 for providing precursorgases, purge gases, carrier gases and other process gases (FIG. 1F). Inother embodiments, conduits 836 and 838, independently, may be in fluidcommunication with separate process gas supplies, including a precursorgas supply, a purge gas supply or a carrier gas supply. Gas conduitassembly 830 contains flanges 832 and 834 on opposite sides of conduit831. Flange 834 is coupled to port 117 on lid support 103 to providefluid communication from port 117 to conduit 831. Also, flange 832 iscoupled to gas inlet 815 on manifold block 806 to provide fluidcommunication from conduit 831 to conduit 884. Isolators 808 aredisposed on manifold block 806 and provide further thermal and electricinsulation for the ground manifold. Isolator 808 may be formed frominsulating material, such as a ceramic material, a quartz material or aderivative thereof. Preferably, isolator 808 is formed from aninsulating polymer, polytetrafluoroethylene (PTFE), such as TEFLON®.

FIGS. 8B-8D illustrate gas conduit 880 extending from gas inlet 811 tochannel conduit 823 within manifold cap assembly 850. The interior ofchannel conduit 823 supports channel 810. A process gas may follow flowpattern 914 through gas conduit 880 and into channel 810 contained inchannel conduit 823. Channel conduit 821 is in fluid communication withand coupled to gas conduit 882 extending from gas inlet 813 and gasconduit 884 extending from gas inlet 815. A process gas following flowpattern 916 through gas conduit 882 and another process gas followingflow pattern 918 through gas conduit 884 may combine within channel 820contained in channel conduit 821 to form a process gas having flowpattern 922 (FIGS. 8C-8D). Gas channel conduits 821 and 823 may besupported by gas channel supports 852 and 854 attached within gasmanifold assembly 800.

In an alternative embodiment, gas conduit 880 and channel conduit 823are external from gas manifold assembly 800. Gas conduit 880 and channelconduit 823 may be in fluid communication directly to insulation cap700, plasma screen insert 600, water box 400 or showerhead 300. Inanother alternative embodiment, gas manifold assembly 800 includes aplurality of electronic control valves (not shown). The electroniccontrol valves as used herein refer to any control valve capable ofproviding rapid and precise gas flow to process chamber 50 with valveopen and close cycles at a rate within a range from about 0.01 secondsto about 10 seconds, preferably from about 0.1 seconds to about 5seconds, for example, a longer cycle may last about 3 seconds and ashorter cycle may last about 0.5 seconds.

In one example, manifold cap assembly 850 has viewing window assembly826 for observing the radiance of a plasma (FIG. 8A). Viewing windowassembly 826 contains lens edge ring 824 encompassing lens 822 and maybe positioned on ledge 814, surrounded by wall surface 816 withinmanifold block 806. In another example, manifold cap assembly 850 maycontain surface 825 that lacks a viewing window (FIG. 1D). Gas conduitassembly 830 may be connected to and in fluid communication with port117 at flange 834 while extended to be connected to and in fluidcommunication with gas inlet 813 on manifold block 806.

In one embodiment, gas conduits 882 and 884 are located adjacent theupper portion of channel conduit 821 and channel 820 (FIGS. 8C-8D, 9Aand 10A). In other embodiments, one or more gas conduits 882 and 884 maybe located along the length of channel 820 between the upper portion ofchannel 820 and insulation cap 700. Not wishing to be bound by theory, aprocess gas flowing from gas conduits 882 and 884 into and throughchannel 820 may form a circular flow pattern, such as flow patterns 922a and 922 b (FIG. 10A). Although the exact geometry of flow pattern 922through channel 820 is not known, it is believed that the process gasmay travel with flow pattern 922 having a vortex flow pattern, a helixflow pattern, a spiral flow pattern, a swirl flow pattern, a twirl flowpattern, a twist flow pattern, a coil flow pattern, a corkscrew flowpattern, a curl flow pattern, a whirlpool flow pattern, or derivativesthereof.

The process gas having flow pattern 922 may be provided within gasregion 920, the combined region of channels 720 and 820 and gas region744 contained within expanding channel 722 (FIG. 9B). In one aspect, thecircular flow patterns of flow pattern 922 may help to establish a moreefficient purge of gas region 920 due to the sweeping action of thecircular flow across the inner surfaces within gas region 920. Thecircular flow pattern of flow pattern 922 also provides a consistent andconformal delivery of process gas across surface 602 of plasma screeninsert 600.

In another embodiment, a process gas passing through gas region 920 withflow pattern 922 is also directed to center portion 601 of plasma screeninsert 600 (FIGS. 9A and 9C). Since center portion 601 is free of holes612, the process gas is directed outwardly, towards holes 612 withinupper surface 602. An obscured pathway between gas region 920 and gasregion 640 for the process gas is efficiently obtained by forming flowpattern 922. The obscured pathway has many advantages over anon-obscured pathway having a line-of-sight between gas region 920 andgas region 640 including a reduction or absence of a secondary plasmathat may be formed between plasma baffle insert 500 and gas manifoldassembly 800 within gas region 920.

Flow pattern 922 forms a vertical flow pattern (i.e., parallel to axis10) since the process gas directional conforms to the angle of holes612. The process gas passes into gas region 640, is directed outwardlyaway from conical nose 520 and into slots 510 or holes 530. The processgas is emitted into process region 60 from slots 510 having flow pattern922 with an injection angle α₁, relative from axis 10, as well as fromholes 530 having flow pattern 912 with an injection angle α₅, relativefrom axis 10 (FIGS. 9B-9D). Slots 510 contained within plasma baffleinsert 500 are positioned at injection angle α₁ to direct a process gashaving a flow pattern at injection angle α₁. Injection angle α₁ of theprocess gas may have an angle within a range from about 20° to about70°, preferably, from about 30° to about 60°, and more preferably, fromabout 40° to about 50°, such as about 45°. Holes 530 contained withinplasma baffle insert 500 are positioned at injection angle α₅ to directa process gas having a flow pattern at injection angle α₅. Injectionangle α₅ of the process gas may have an angle within a range from about0° to about 60°, preferably, from about 15° to about 50°, and morepreferably, from about 30° to about 40°, such as about 35°. Therefore,flow pattern 922 of the process gas may have a circular pathwayinherited from the injection angle α₁ of slots 510. The circular pathwayusually has a vortex geometry, a helix geometry, a spiral geometry, or aderivative thereof. Also, flow pattern 912 of the process gas may have aconical pathway inherited from the injection angle α₅ of holes 530.Process gas having flow pattern 912 may be directed to the center ofsubstrate 8. A substrate within process region 60 may be exposed to theprocess gas having flow patterns 912 and 922.

Also, the injection angle α₁ of slots 510 forms a secondary obscuredpathway for the process gas, which is between gas region 640 and processregion 60. The secondary obscured pathway further assist the reductionor avoidance of a secondary plasma that may be formed between plasmabaffle insert 500 and gas manifold assembly 800 within gas region 920 orwithin openings 506 on upper surface 503 of plasma baffle insert 500.

In another embodiment, a process gas may have flow pattern 914 whilepassing through gas region 910, the combined region of channels 710 and810 and gas region 742 contained within groove 725 (FIG. 9B). Once theprocess gas enter gas region 742, flow pattern 914 is altered as theprocess gas is directed around plasma screen insert 600 along circularpath 923 (FIG. 9A). The process gas is outwardly directed through slots614 on plasma screen insert 600 and into gas region 441. An obscuredpathway for flow pattern 914 of the process gas is formed between gasregion 910 and gas region 441. The obscured pathway has advantages overa non-obscured pathway having a line-of-sight between gas region 910 andgas region 441 including a reduction or absence of a secondary plasmathat may be formed between showerhead 300 and gas manifold assembly 800within gas region 910.

Flow pattern 914 proceeds from gas region 441 with a downwardly flowpattern since the process gas directional conforms to the angle ofpassageways 440 within water box 400. The process gas passes into gasregion 540, is directed outwardly and across upper surface 303 ofshowerhead 300. The process gas is emitted into process region 60 fromholes 310 having flow pattern 914 parallel or substantially parallel ofaxis 10 (FIG. 9B). A substrate within process region 60 may be exposedto the process gas having flow pattern 914. A secondary obscured pathwayfor the process gas is formed from gas region 441, to gas region 540 andinto process region 60. The secondary obscured pathway further assistthe reduction or avoidance of a secondary plasma that may be formedbetween showerhead 300 and gas manifold assembly 800 within gas region910.

A process gas having circular pathways of flow pattern 922 may be formedby flowing a single process gas or multiple process gases into gasregion 820 (FIGS. 10A-10C). In one embodiment, FIG. 10A reveals a topcross-sectional view into channel 820 of channel conduit 821 which isadapted to receive a process gas from gas conduit 882 and a process gasfrom gas conduit 884. Gas conduit 882 and gas conduit 884 are eachcoupled to an individual process gas source. Gas conduits 882 and 884may each be positioned independently at angle α₄, measured from centerline 915 a of gas conduit 884 or center line 915 b of gas conduit 882 toradius line 917 from the center of channel conduit 821, such as axis 10.Gas conduits 882 and 884 may be positioned to have an angle α₄ (i.e.,when α₄>0°) for flowing process gases together in a circular direction,such as flow patterns 922 a and 922 b. Flow patterns 922 a and 922 bform flow pattern 922 of a process gas passing through channel 820 witha vortex pattern. In one aspect, the circular flow patterns of flowpattern 922 may help to establish a more efficient purge of processregion 60 due to the sweeping action of the circular flow acrossinterior surfaces. Also, the circular flow patterns of flow pattern 922provide a consistent and conformal delivery of process gas to slots 510.

In an alternative embodiment, FIG. 10B is a top cross-sectional view ofchannel 820 and channel conduit 1021 which is adapted to receive asingle gas flow through gas conduit 1084 coupled to a process gassource. Gas conduit 1084 may be positioned at angle α₄ from center line915 a of gas conduit 1084 and from radius line 917 from the center ofchannel conduit 1021, such as axis 10. Gas conduit 1084 may bepositioned having angle α₄ (i.e., when α₄>0°) to cause a process gas toflow in a circular direction, such as flow pattern 922 a and to continuethrough channel 820 with a vortex pattern.

In another alternative embodiment, FIG. 10C is a top cross-sectionalview into channel 820 of channel conduit 1021 which is adapted toreceive three gas flows together, partially together (i.e., two of threegas flows together), or separately through three gas inlets, such as gasconduits 1082, 1084 and 1086, each coupled to an individual process gassource. Each one of gas conduits 1082, 1084 and 1086 may be positionedindependently at angle α₄ from center lines 915 a, 915 b and 915 c ofgas conduits 1082, 1084 and 1086 and from radius line 917 from thecenter of channel conduit 1021, such as axis 10. Each one of gasconduits 1082, 1084 and 1086 may be positioned having angle α₄ (i.e.,when α₄>0°) to cause process gases to flow together in a circulardirection, such as flow patterns 922 a, 922 b and 922 c and to continuethrough channel 820 with a vortex pattern. Further disclosure foradapting process chamber 50 to flow three or more process gas flows isdescribed in commonly assigned U.S. Pat. No. 6,916,398, which isincorporated herein by reference.

In an example for forming a high-k material, the three gas flows maycontain a hafnium precursor, a silicon precursor and an oxidizing gas,where, the first flow includes TDEAH, TDMAH, or HfCl₄, the second flowincludes TDMAS, Tris-DMAS or silane and the third flow includes anoxidizing gas containing water vapor from a water vapor generator (WVG)system. Further disclosure for a process to form high-k materials thatmay be used with process chamber 50 is described in commonly assignedand co-pending U.S. Ser. No. 11/127,767, filed May 12, 2005, entitled“Apparatus and Methods for Atomic Layer Deposition of Hafnium-ContainingHigh-k Materials,” and published as US 2005-0271813, which isincorporated herein by reference.

In an alternative embodiment, conduit system 34 may further containprecursor reservoirs gradually expanding gas conduits forming nozzles atthe ends that are also positioned in fluid communication with gas inlets811, 813 and 815. The nozzles or ends that are useful in someembodiments described herein are further described in commonly assignedU.S. patent Ser. No. 11/119,388, filed Apr. 29, 2005, entitled, “Controlof Gas Flow and Delivery to Suppress the Formation of Particles in anMOCVD/ALD System,” and published as US 2005-0252449, which isincorporated herein by reference to support disclosure of the precursorreservoirs and the gradually expanding gas conduits. The gas conduitgeometry prevents large temperature drops by providing passing gases ameans to gradually expand through an increasing tapered flow channel. Inone embodiment, the flow channel transitions from the cross-sections ofdelivery gas lines with internal diameter within a range from about 3 mmto about 15 mm to gas inlets 811, 813 and 815 with a larger diameterwithin a range from about 10 mm to about 20 mm over a distance within arange from about 30 mm to about 100 mm. A gradual increase of thediameter of a flow channel allows the expanding gases to be in nearequilibrium and prevents a rapid lost of heat to maintain asubstantially constant temperature. Expanding gas conduits may compriseone or more tapered inner surfaces such as a tapered straight surface, aconcave surface, a convex surface, derivatives thereof or combinationsthereof or may comprise sections of one or more tapered inner surfaces(e.g., a portion tapered and a portion non-tapered).

Ruthenium ALD Process

Embodiments of the invention provide methods for depositing a variety ofmaterial (e.g., ruthenium materials) on a substrate by a vapordeposition process, such as atomic layer deposition (ALD) orplasma-enhanced ALD (PE-ALD). In one aspect, the process has little orno initiation delay and maintains a fast deposition rate while forming aruthenium material. The ruthenium material is deposited with good stepcoverage, strong adhesion and contains a low carbon concentration forhigh electrical conductivity.

In one embodiment, a ruthenium material may be formed during a PE-ALDprocess containing a constant flow of a reagent gas while providingsequential pulses of a ruthenium precursor and a plasma. In anotherembodiment, a ruthenium material may be formed during another PE-ALDprocess that provides sequential pulses of a ruthenium precursor and areagent plasma. In both of these embodiments, the reagent is generallyionized during the process. Also, the PE-ALD process provides that theplasma may be generated external from the process chamber, such as by aremote plasma generator (RPS) system, or preferably, the plasma may begenerated in situ a plasma capable ALD process chamber. During PE-ALDprocesses, a plasma may be generated from a microwave (MW) frequencygenerator or a radio frequency (RF) generator. In a preferred example,an in situ plasma is generated by a RF generator, such as within processchamber 50 or with lid assembly 100. In another embodiment, a rutheniummaterial may be formed during a thermal ALD process that providessequential pulses of a ruthenium precursor and a reagent.

An ALD process chamber used during embodiments described herein may beprocess chamber 50, as described above, or another chamber body adaptedto receive lid assembly 100, any portion or component of lid assembly100 or a derivative thereof. Other ALD process chambers may also be usedduring some of the embodiments described herein and are available fromApplied Materials, Inc., located in Santa Clara, Calif. A detaileddescription of an ALD process chamber may be found in commonly assignedU.S. Pat. Nos. 6,916,398 and 6,878,206, and commonly assigned,co-pending U.S. patent application Ser. No. 10/281,079, entitled “GasDelivery Apparatus for Atomic Layer Deposition”, filed on Oct. 25, 2002,and published as US 2003-0121608, which are hereby incorporated byreference in their entirety. In another embodiment, a chamber configuredto operate in both an ALD mode as well as a conventional CVD mode may beused to deposit ruthenium materials is described in commonly assignedand co-pending U.S. Ser. No. 10/712,690, entitled “Apparatus and Methodfor Hybrid Chemical Processing,” filed on Nov. 13, 2003, and publishedas US 2004-0144311, which are each incorporated herein by reference intheir entirety.

The ALD process provides that the process chamber may be pressurized ata pressure within a range from about 0.1 Torr to about 80 Torr,preferably from about 0.5 Torr to about 10 Torr, and more preferably,from about 1 to about 5. Also, the chamber or the substrate may beheated to a temperature of less than about 500° C., preferably within arange from about 100° C. to about 450° C., and more preferably, fromabout 150° C. to about 400° C., for example, about 300° C. During PE-ALDprocesses, a plasma is ignited within the process chamber for an in situplasma process, or alternative, may be formed by an external source,such as a remote plasma generator (RPS) system. A plasma may begenerated a MW generator, but preferably by a RF generator. For example,a plasma may be ignited within process chamber 50 or with lid assembly100. The RF generator may be set at a frequency within a range fromabout 100 KHz to about 1.6 MHz. In one example, a RF generator, with afrequency of 13.56 MHz, may be set to have a power output within a rangefrom about 100 watts to about 1,000 watts, preferably, from about 250watts to about 600 watts, and more preferably, from about 300 watts toabout 500 watts. In one example, a RF generator, with a frequency of 400KHz, may be set to have a power output within a range from about 200watts to about 2,000 watts, preferably, from about 500 watts to about1,500 watts. A surface of substrate may be exposed to a plasma having apower per surface area value within a range from about 0.01 watts/cm² toabout 10.0 watts/cm², preferably, from about 0.05 watts/cm² to about 6.0watts/cm².

The substrate may be for example, a silicon substrate having aninterconnect pattern defined in one or more dielectric material layersformed thereon. In example, the substrate contains a barrier layerthereon, while in another example, the substrate contains a dielectricsurface. The process chamber conditions such as, the temperature andpressure, are adjusted to enhance the adsorption of the process gases onthe substrate so as to facilitate the reaction of the pyrrolyl rutheniumprecursors and the reagent gas.

In one embodiment, the substrate may be exposed to a reagent gasthroughout the whole ALD cycle. The substrate may be exposed to aruthenium precursor gas formed by passing a carrier gas (e.g., nitrogenor argon) through an ampoule of a ruthenium precursor. The ampoule maybe heated depending on the ruthenium precursor used during the process.In one example, an ampoule containing (MeCp)(Py)Ru may be heated to atemperature within a range from about 60° C. to about 100° C., such as80° C. The ruthenium precursor gas usually has a flow rate within arange from about 100 sccm to about 2,000 sccm, preferably, from about200 sccm to about 1,000 sccm, and more preferably, from about 300 sccmto about 700 sccm, for example, about 500 sccm. The ruthenium precursorgas and the reagent gas may be combined to form a deposition gas. Areagent gas usually has a flow rate within a range from about 100 sccmto about 3,000 sccm, preferably, from about 200 sccm to about 2,000sccm, and more preferably, from about 500 sccm to about 1,500 sccm. Inone example, ammonia is used as a reagent gas with a flow rate of about1,500 sccm. The substrate may be exposed to the ruthenium precursor gasor the deposition gas containing the ruthenium precursor and the reagentgas for a time period within a range from about 0.1 seconds to about 8seconds, preferably, from about 1 second to about 5 seconds, and morepreferably, from about 2 seconds to about 4 seconds. The flow of theruthenium precursor gas may be stopped once the ruthenium precursor isadsorbed on the substrate. The ruthenium precursor may be adiscontinuous layer, continuous layer or even multiple layers.

The substrate and chamber may be exposed to a purge step after stoppingthe flow of the ruthenium precursor gas. The flow rate of the reagentgas may be maintained or adjusted from the previous step during thepurge step. Preferably, the flow of the reagent gas is maintained fromthe previous step. Optionally, a purge gas may be administered into theprocess chamber with a flow rate within a range from about 100 sccm toabout 2,000 sccm, preferably, from about 200 sccm to about 1,000 sccm,and more preferably, from about 300 sccm to about 700 sccm, for example,about 500 sccm. The purge step removes any excess ruthenium precursorand other contaminants within the process chamber. The purge step may beconducted for a time period within a range from about 0.1 seconds toabout 8 seconds, preferably, from about 1 second to about 5 seconds, andmore preferably, from about 2 seconds to about 4 seconds. The carriergas, the purge gas and the process gas may contain nitrogen, hydrogen,ammonia, argon, neon, helium or combinations thereof. In a preferredembodiment, the carrier gas contains nitrogen.

Thereafter, the flow of the reagent gas may be maintained or adjustedbefore igniting a plasma. The substrate may be exposed to the plasma fora time period within a range from about 0.1 seconds to about 20 seconds,preferably, from about 1 second to about 10 seconds, and morepreferably, from about 2 seconds to about 8 seconds. Thereafter, theplasma power was turned off. In one example, the reagent may be ammonia,nitrogen, hydrogen or a combination thereof to form an ammonia plasma, anitrogen plasma, a hydrogen plasma or a combined plasma. The reactantplasma reacts with the adsorbed ruthenium precursor on the substrate toform a ruthenium material thereon. In one example, the reactant plasmais used as a reductant to form metallic ruthenium. However, a variety ofreactants may be used to form ruthenium materials having a wide range ofcompositions. In one example, a boron-containing reactant compound(e.g., diborane) is used to form a ruthenium material containing boride.In another example, a silicon-containing reactant compound (e.g.,silane) is used to form a ruthenium material containing silicide.

The process chamber was exposed to a second purge step to remove excessprecursors or contaminants from the previous step. The flow rate of thereagent gas may be maintained or adjusted from the previous step duringthe purge step. An optional purge gas may be administered into theprocess chamber with a flow rate within a range from about 100 sccm toabout 2,000 sccm, preferably, from about 200 sccm to about 1,000 sccm,and more preferably, from about 300 sccm to about 700 sccm, for example,about 500 sccm. The second purge step may be conducted for a time periodwithin a range from about 0.1 seconds to about 8 seconds, preferably,from about 1 second to about 5 seconds, and more preferably, from about2 seconds to about 4 seconds.

The ALD cycle may be repeated until a predetermined thickness of theruthenium material is deposited on the substrate. The ruthenium materialmay be deposited with a thickness less than 1,000 Å, preferably lessthan 500 Å and more preferably from about 10 Å to about 100 Å, forexample, about 30 Å. The processes as described herein may deposit aruthenium material at a rate of at least 0.15 Å/cycle, preferably, atleast 0.25 Å/cycle, more preferably, at least 0.35 Å/cycle or faster. Inanother embodiment, the processes as described herein overcomeshortcomings of the prior art relative as related to nucleation delay.There is no detectable nucleation delay during many, if not most, of theexperiments to deposit the ruthenium materials.

In another embodiment, a ruthenium material may be formed during anotherPE-ALD process that provides sequentially exposing the substrate topulses of a ruthenium precursor and an active reagent, such as a reagentplasma. The substrate may be exposed to a ruthenium precursor gas formedby passing a carrier gas through an ampoule containing a rutheniumprecursor, as described herein. The ruthenium precursor gas usually hasa flow rate within a range from about 100 sccm to about 2,000 sccm,preferably, from about 200 sccm to about 1,000 sccm, and morepreferably, from about 300 sccm to about 700 sccm, for example, about500 sccm. The substrate may be exposed to the deposition gas containingthe ruthenium precursor and the reagent gas for a time period within arange from about 0.1 seconds to about 8 seconds, preferably, from about1 second to about 5 seconds, and more preferably from about 2 seconds toabout 4 seconds. The flow of the ruthenium precursor gas may be stoppedonce the ruthenium precursor is adsorbed on the substrate. The rutheniumprecursor may be a discontinuous layer, continuous layer or evenmultiple layers.

Subsequently, the substrate and chamber are exposed to a purge step. Apurge gas may be administered into the process chamber during the purgestep. In one aspect, the purge gas is the reagent gas, such as ammonia,nitrogen or hydrogen. In another aspect, the purge gas may be adifferent gas than the reagent gas. For example, the reagent gas may beammonia and the purge gas may be nitrogen, hydrogen or argon. The purgegas may have a flow rate within a range from about 100 sccm to about2,000 sccm, preferably, from about 200 sccm to about 1,000 sccm, andmore preferably, from about 300 sccm to about 700 sccm, for example,about 500 sccm. The purge step removes any excess ruthenium precursorand other contaminants within the process chamber. The purge step may beconducted for a time period within a range from about 0.1 seconds toabout 8 seconds, preferably, from about 1 second to about 5 seconds, andmore preferably, from about 2 seconds to about 4 seconds. A carrier gas,a purge gas and a process gas may contain nitrogen, hydrogen, ammonia,argon, neon, helium or combinations thereof.

The substrate and the adsorbed ruthenium precursor thereon may beexposed to the reagent gas during the next step of the ALD process.Optionally, a carrier gas may be administered at the same time as thereagent gas into the process chamber. The reagent gas may be ignited toform a plasma. The reagent gas usually has a flow rate within a rangefrom about 100 sccm to about 3,000 sccm, preferably, from about 200 sccmto about 2,000 sccm, and more preferably, from about 500 sccm to about1,500 sccm. In one example, ammonia is used as a reagent gas with a flowrate of about 1,500 sccm. The substrate may be exposed to the plasma fora time period within a range from about 0.1 seconds to about 20 seconds,preferably, from about 1 second to about 10 seconds, and morepreferably, from about 2 seconds to about 8 seconds. Thereafter, theplasma power may be turned off. In one example, the reagent may beammonia, nitrogen, hydrogen or combinations thereof, while the plasmamay be an ammonia plasma, a nitrogen plasma, a hydrogen plasma or acombination thereof. The reactant plasma reacts with the adsorbedruthenium precursor on the substrate to form a ruthenium materialthereon. Preferably, the reactant plasma is used as a reductant to formmetallic ruthenium. However, a variety of reactants may be used to formruthenium materials having a wide range of compositions, as describedherein.

The process chamber may be exposed to a second purge step to removeexcess precursors or contaminants from the process chamber. The flow ofthe reagent gas may have been stopped at the end of the previous stepand started during the purge step, if the reagent gas is used as a purgegas. Alternative, a purge gas that is different than the reagent gas maybe administered into the process chamber. The reagent gas or purge gasmay have a flow rate within a range from about 100 sccm to about 2,000sccm, preferably, from about 200 sccm to about 1,000 sccm, and morepreferably, from about 300 sccm to about 700 sccm, for example, about500 sccm. The second purge step may be conducted for a time periodwithin a range from about 0.1 seconds to about 8 seconds, preferably,from about 1 second to about 5 seconds, and more preferably, from about2 seconds to about 4 seconds.

The ALD cycle may be repeated until a predetermined thickness of theruthenium material is deposited on the substrate. The ruthenium materialmay be deposited with a thickness less than 1,000 Å, preferably lessthan 500 Å and more preferably from about 10 Å to about 100 Å, forexample, about 30 Å. The processes as described herein may deposit aruthenium material at a rate of at least 0.15 Å/cycle, preferably, atleast 0.25 Å/cycle, more preferably, at least 0.35 Å/cycle or faster. Inanother embodiment, the processes as described herein overcomeshortcomings of the prior art relative as related to nucleation delay.There is no detectable nucleation delay during many, if not most, of theexperiments to deposit the ruthenium materials.

Generally, in order to use a ruthenocene compound during an ALD process,a surface treatment step is required, unless the surface is terminatedwith a hydroxyl group, such as —OH, or an electron-rich surface, such asa metallic layer. On a barrier layer such as tantalum nitride,ruthenocene precursors do not deposit ruthenium materials via ALDprocesses without a pre-treatment step. Even with a pre-treatment step,such as the hydroxylation of the barrier surface, the randomly placednucleation sites cause ruthenocene to form satellites or islands ofruthenium during the deposition process. Therefore, an ALD process usinga ruthenocene precursor generally deposits a ruthenium material havingan increased electrical resistance, probably due to the unevenness ofthe ruthenium material. Also, the deposition process may suffer anucleation delay due to the ruthenocene precursor. Furthermore, a highadsorption temperature above 400° C. is usually required for ruthenoceneprecursors. Such a high temperatures may damage device structure withina sensitive low-k dielectric environment, for example, within a copperback end of line (BEOL) process. Hence, it is preferred to perform ALDprocesses at a temperature less than 400° C., preferably, less than 350°C. Further, ruthenium materials deposited from ruthenocene precursorsused during an ALD process on dielectric surfaces tend to fail tapetesting due to the low adhesion of the underlying layer. Therefore, inmany embodiments, ruthenocene compounds, such asbis(ethylcyclopentadienyl) ruthenium, bis(cyclopentadienyl) rutheniumand bis(pentamethylcyclopentadienyl) ruthenium are less desirableruthenium precursors.

Embodiments of the invention include improved methodologies overcomingdisadvantages of the prior art, and preferred precursors and chemistriesproviding additional advantages over the prior art. A family ofruthenium precursors useful to form a ruthenium material during thedeposition process described herein includes pyrrolyl rutheniumprecursors. A further disclosure of ALD processes for depositingruthenium materials is described in commonly assigned and co-pendingU.S. Ser. No. 11/470,466, filed Sep. 6, 2006, and entitled “Atomic LayerDeposition Process for Ruthenium Materials,” which is incorporatedherein in its entirety by reference. The pyrrolyl ligand provides thepyrrolyl ruthenium precursor advantages over previous rutheniumprecursors (e.g., ruthenocene and derivatives thereof) during an ALDprocess. The pyrrolyl ligand is more thermodynamically stable than manyligands, as well as forms a very volatile chemical precursor. A pyrrolylruthenium precursor contains ruthenium and at least one pyrrolyl ligandor at least one pyrrolyl derivative ligand. A pyrrolyl rutheniumprecursor may have a pyrrolyl ligand, such as:

where R₁, R₂, R₃, R₄ and R₅ are each independently hydrogen, an alkylgroup (e.g., methyl, ethyl, propyl, butyl, amyl or higher), an aminegroup, an alkoxy group, an alcohol group, an aryl group, anotherpyrrolyl group (e.g., 2,2′-bipyrrolyl), a pyrazole group, derivativesthereof or combinations thereof. The pyrrolyl ligand may have any two ormore of R₁, R₂, R₃, R₄ and R₅ connected together by a chemical group.For example, R₂ and R₃ may be a portion of a ring structure such as anindolyl group or derivative thereof. A pyrrolyl ruthenium precursor asused herein refers to any chemical compound containing ruthenium and atleast one pyrrolyl ligand or at least one derivative of a pyrrolylligand. In preferred examples, a pyrrolyl ruthenium precursor mayinclude bis(tetramethylpyrrolyl) ruthenium, bis(2,5-dimethylpyrrolyl)ruthenium, bis(2,5-diethylpyrrolyl) ruthenium, bis(tetraethylpyrrolyl)ruthenium, pentadienyl tetramethylpyrrolyl ruthenium, pentadienyl2,5-dimethylpyrrolyl ruthenium, pentadienyl tetraethylpyrrolylruthenium, pentadienyl 2,5-diethylpyrrolyl ruthenium,1,3-dimethylpentadienyl pyrrolyl ruthenium, 1,3-diethylpentadienylpyrrolyl ruthenium, methylcyclopentadienyl pyrrolyl ruthenium,ethylcyclopentadienyl pyrrolyl ruthenium, 2-methylpyrrolyl pyrrolylruthenium, 2-ethylpyrrolyl pyrrolyl ruthenium or a derivative thereof.

An important precursor characteristic is to have a favorable vaporpressure. Deposition precursors may have gas, liquid or solid states atambient temperature and pressure. However, within the ALD chamber,precursors are usually volatilized as gas or plasma. Precursors areusually heated prior to delivery into the process chamber. Although manyvariables affect the deposition rate during an ALD process to formruthenium material, the size of the ligand on a pyrrolyl rutheniumprecursor is an important consideration in order to achieve apredetermined deposition rate. The size of the ligand does contribute todetermining the specific temperature and pressure required to vaporizethe pyrrolyl ruthenium precursor. Furthermore, a pyrrolyl rutheniumprecursor has a particular ligand steric hindrance proportional to thesize of the ligands. In general, larger ligands provide more sterichindrance. Therefore, less molecules of a precursor more bulky ligandsmay be adsorbed on a surface during the half reaction while exposing thesubstrate to the precursor than if the precursor contained less bulkyligands. The steric hindrance effect limits the amount of adsorbedprecursors on the surface. Therefore, a monolayer of a pyrrolylruthenium precursor may be formed to contain a more molecularlyconcentrated by decreasing the steric hindrance of the ligand(s). Theoverall deposition rate is proportionally related to the amount ofadsorbed precursor on the surface, since an increased deposition rate isusually achieved by having more of the precursor adsorbed to thesurface. Ligands that contain smaller functional groups (e.g., hydrogenor methyl) generally provide less steric hindrance than ligands thatcontain larger functional groups (e.g., aryl). Also, the position on theligand motif may affect the steric hindrance of the precursor.Generally, the inner positions, R₂ and R₅, have less affect than doesthe outer positions R₃ and R₄. For example, a pyrrolyl rutheniumprecursor containing R₂ and R₅ equal to hydrogen groups and R₃ and R₄equal to methyl groups has more steric hindrance than a pyrrolylruthenium precursor containing R₂ and R₅ equal to methyl groups and R₃and R₄ equal to hydrogen groups.

A pyrrolyl ligand may be abbreviated by “py” and a pyrrolyl derivativeligand may be abbreviated by “R-py.” Exemplary pyrrolyl rutheniumprecursors useful to form a ruthenium material during the depositionprocess described herein include alkyl pyrrolyl ruthenium precursors(e.g., (R_(x)-py)Ru), bis(pyrrolyl) ruthenium precursors (e.g., (py)₂Ru)and dienyl pyrrolyl ruthenium precursors (e.g., (Cp)(py)Ru). Examples ofalkyl pyrrolyl ruthenium precursors include methylpyrrolyl ruthenium,ethylpyrrolyl ruthenium, propylpyrrolyl ruthenium, dimethylpyrrolylruthenium, diethylpyrrolyl ruthenium, dipropylpyrrolyl ruthenium,trimethylpyrrolyl ruthenium, triethylpyrrolyl ruthenium,tetramethylpyrrolyl ruthenium, tetraethylpyrrolyl ruthenium orderivatives thereof. Examples of bis(pyrrolyl) ruthenium precursorsinclude bis(pyrrolyl) ruthenium, bis(methylpyrrolyl) ruthenium,bis(ethylpyrrolyl) ruthenium, bis(propylpyrrolyl) ruthenium,bis(dimethylpyrrolyl) ruthenium, bis(diethylpyrrolyl) ruthenium,bis(dipropylpyrrolyl) ruthenium, bis(trimethylpyrrolyl) ruthenium,bis(triethylpyrrolyl) ruthenium, bis(tetramethylpyrrolyl) ruthenium,bis(tetraethylpyrrolyl) ruthenium, methylpyrrolyl pyrrolyl ruthenium,ethylpyrrolyl pyrrolyl ruthenium, propylpyrrolyl pyrrolyl ruthenium,dimethylpyrrolyl pyrrolyl ruthenium, diethylpyrrolyl pyrrolyl ruthenium,dipropylpyrrolyl pyrrolyl ruthenium, trimethylpyrrolyl pyrrolylruthenium, triethylpyrrolyl pyrrolyl ruthenium, tetramethylpyrrolylpyrrolyl ruthenium, tetraethylpyrrolyl pyrrolyl ruthenium or derivativesthereof.

A dienyl pyrrolyl ruthenium precursor contains at least one dienylligand and at least one pyrrolyl ligand. The dienyl ligand may contain acarbon backbone with as little as four carbon atoms or as many as aboutten carbon atoms, preferably, about five or six. The dienyl ligand mayhave a ring structure (e.g., cyclopentadienyl) or may be an open alkylchain (e.g., pentadienyl). Also, dienyl ligand may contain no alkylgroups, one alkyl group or many alkyl groups.

In one embodiment, the dienyl pyrrolyl ruthenium precursor contains apentadienyl ligand or an alkylpentadienyl ligand. Examples ofpentadienyl pyrrolyl ruthenium precursors include pentadienyl pyrrolylruthenium, pentadienyl methylpyrrolyl ruthenium, pentadienylethylpyrrolyl ruthenium, pentadienyl propylpyrrolyl ruthenium,pentadienyl dimethylpyrrolyl ruthenium, pentadienyl diethylpyrrolylruthenium, pentadienyl dipropylpyrrolyl ruthenium, pentadienyltrimethylpyrrolyl ruthenium, pentadienyl triethylpyrrolyl ruthenium,pentadienyl tetramethylpyrrolyl ruthenium, pentadienyltetraethylpyrrolyl ruthenium or derivatives thereof. Examples ofalkylpentadienyl pyrrolyl ruthenium precursors include alkylpentadienylpyrrolyl ruthenium, alkylpentadienyl methylpyrrolyl ruthenium,alkylpentadienyl ethylpyrrolyl ruthenium, alkylpentadienylpropylpyrrolyl ruthenium, alkylpentadienyl dimethylpyrrolyl ruthenium,alkylpentadienyl diethylpyrrolyl ruthenium, alkylpentadienyldipropylpyrrolyl ruthenium, alkylpentadienyl trimethylpyrrolylruthenium, alkylpentadienyl triethylpyrrolyl ruthenium, alkylpentadienyltetramethylpyrrolyl ruthenium, alkylpentadienyl tetraethylpyrrolylruthenium or derivatives thereof.

In another embodiment, the dienyl pyrrolyl ruthenium precursor containsa cyclopentadienyl ligand or an alkylcyclopentadienyl ligand. Examplesof cyclopentadienyl pyrrolyl ruthenium precursors includecyclopentadienyl pyrrolyl ruthenium, cyclopentadienyl methylpyrrolylruthenium, cyclopentadienyl ethylpyrrolyl ruthenium, cyclopentadienylpropylpyrrolyl ruthenium, cyclopentadienyl dimethylpyrrolyl ruthenium,cyclopentadienyl diethylpyrrolyl ruthenium, cyclopentadienyldipropylpyrrolyl ruthenium, cyclopentadienyl trimethylpyrrolylruthenium, cyclopentadienyl triethylpyrrolyl ruthenium, cyclopentadienyltetramethylpyrrolyl ruthenium, cyclopentadienyl tetraethylpyrrolylruthenium or derivatives thereof. Examples of alkylcyclopentadienylpyrrolyl ruthenium precursors include alkylcyclopentadienyl pyrrolylruthenium, alkylcyclopentadienyl methylpyrrolyl ruthenium,alkylcyclopentadienyl ethyl pyrrolyl ruthenium, alkylcyclopentadienylpropylpyrrolyl ruthenium, alkylcyclopentadienyl dimethylpyrrolylruthenium, alkylcyclopentadienyl diethylpyrrolyl ruthenium,alkylcyclopentadienyl dipropylpyrrolyl ruthenium, alkylcyclopentadienyltrimethylpyrrolyl ruthenium, alkylcyclopentadienyl triethylpyrrolylruthenium, alkylcyclopentadienyl tetramethylpyrrolyl ruthenium,alkylcyclopentadienyl tetraethylpyrrolyl ruthenium or derivativesthereof.

In another embodiment, a ruthenium precursor may not contain a pyrrolylligand or a pyrrolyl derivative ligand, but instead, contain at leastone open chain dienyl ligand, such as CH₂CRCHCRCH₂, where R isindependently an alkyl group or hydrogen. A ruthenium precursor may havetwo open-chain dienyl ligands, such as pentadienyl or heptadienyl. Abis(pentadienyl) ruthenium compound has a generic chemical formula(CH₂CRCHCRCH₂)₂Ru, where R is independently an alkyl group or hydrogen.Usually, R is independently hydrogen, methyl, ethyl, propyl or butyl.Therefore, ruthenium precursors may include bis(dialkylpentadienyl)ruthenium compounds, bis(alkylpentadienyl) ruthenium compounds,bis(pentadienyl) ruthenium compounds or combinations thereof. Examplesof ruthenium precursors include bis(2,4-dimethylpentadienyl) ruthenium,bis(2,4-diethylpentadienyl) ruthenium, bis(2,4-diisopropylpentadienyl)ruthenium, bis(2,4-ditertbutylpentadienyl) ruthenium,bis(methylpentadienyl) ruthenium, bis(ethylpentadienyl) ruthenium,bis(isopropylpentadienyl) ruthenium, bis(tertbutylpentadienyl)ruthenium, derivatives thereof or combinations thereof. In someembodiments, other ruthenium precursors includetris(2,2,6,6-tetramethyl-3,5-heptanedionato) ruthenium, dicarbonylpentadienyl ruthenium, ruthenium acetyl acetonate,2,4-dimethylpentadienyl cyclopentadienyl ruthenium,bis(2,2,6,6-tetramethyl-3,5-heptanedionato) (1,5-cyclooctadiene)ruthenium, 2,4-dimethylpentadienyl methylcyclopentadienyl ruthenium,1,5-cyclooctadiene cyclopentadienyl ruthenium, 1,5-cyclooctadienemethylcyclopentadienyl ruthenium, 1,5-cyclooctadieneethylcyclopentadienyl ruthenium, 2,4-dimethylpentadienylethylcyclopentadienyl ruthenium, 2,4-dimethylpentadienylisopropylcyclopentadienyl ruthenium, bis(N,N-dimethyl 1,3-tetramethyldiiminato) 1,5-cyclooctadiene ruthenium, bis(N,N-dimethyl 1,3-dimethyldiiminato) 1,5-cyclooctadiene ruthenium, bis(allyl) 1,5-cyclooctadieneruthenium, η⁶-C₆H₆ 1,3-cyclohexadiene ruthenium,bis(1,1-dimethyl-2-aminoethoxylato) 1,5-cyclooctadiene ruthenium,bis(1,1-dimethyl-2-aminoethylaminato) 1,5-cyclooctadiene ruthenium,derivatives thereof, or combinations thereof.

The various ruthenium precursors containing a pyrrolyl ligand, an openchain dienyl ligand or a combination thereof may be used with at leastone reagent to form a ruthenium material. The ruthenium precursor andthe reagent may be sequentially introduced into the process chamberduring a thermal ALD process or a PE-ALD process. A suitable reagent forforming a ruthenium material may be a reducing gas and include hydrogen(e.g., H₂ or atomic-H), atomic-N, ammonia (NH₃), hydrazine (N₂H₄),silane (SiH₄), disilane (Si₂H₆), trisilane (Si₃H₈), tetrasilane(Si₄H₁₀), dimethylsilane (SiC₂H₈), methyl silane (SiCH₆), ethylsilane(SiC₂H₈), chlorosilane (ClSiH₃), dichlorosilane (Cl₂SiH₂),hexachlorodisilane (Si₂Cl₆), borane (BH₃), diborane (B₂H₆), triborane,tetraborane, pentaborane, triethylborane (Et₃B), derivatives thereof,plasmas thereof, or combinations thereof.

In an alternative embodiment, the reagent gas may includeoxygen-containing gases, such as oxygen (e.g., O₂), nitrous oxide (N₂O),nitric oxide (NO), nitrogen dioxide (NO₂), derivatives thereof orcombinations thereof. Furthermore, the traditional reductants may becombined with the oxygen-containing reagents to form a reagent gas.Oxygen-containing gases that may be used during deposition processes toform ruthenium materials have traditionally been used in the chemicalart as an oxidant. However, ligands on a metal-organic compoundcontaining a noble metal (e.g., Ru) are usually more susceptible to theoxygen-containing reductants than the noble metal. Therefore, the ligandis generally oxidized from the metal center while the metal ion isreduced to form the elemental metal. In one embodiment, the reagent gascontains ambient oxygen from the air that may be dried over sieves toreduce ambient water. Further disclosure useful for processes describedherein, including a process for depositing a ruthenium material by usingan oxygen-containing gas, is further described in commonly assigned andco-pending U.S. Ser. No. 10/811,230, entitled “Ruthenium Layer Formationfor Copper Film Deposition,” filed Mar. 26, 2004, and published as US2004-0241321, which is incorporated herein in its entirety by reference.

The time interval for the pulse of the ruthenium precursor is variabledepending upon a number of factors such as, for example, the volumecapacity of the process chamber employed, the vacuum system coupledthereto and the volatility/reactivity of the reactants used during theALD process. For example, (1) a large-volume process chamber may lead toa longer time to stabilize the process conditions such as, for example,carrier/purge gas flow and temperature, requiring a longer pulse time;(2) a lower flow rate for the process gas may also lead to a longer timeto stabilize the process conditions requiring a longer pulse time; and(3) a lower chamber pressure means that the process gas is evacuatedfrom the process chamber more quickly requiring a longer pulse time. Ingeneral, the process conditions are advantageously selected so that apulse of the ruthenium precursor provides a sufficient amount ofprecursor so that at least a monolayer of the ruthenium precursor isadsorbed on the substrate. Thereafter, excess ruthenium precursorremaining in the chamber may be removed from the process chamber by theconstant carrier gas stream in combination with the vacuum system.

The time interval for each of the pulses of the ruthenium precursor andthe reagent gas may have the same duration. That is, the duration of thepulse of the ruthenium precursor may be identical to the duration of thepulse of the reagent gas. For such an embodiment, a time interval (T₁)for the pulse of the ruthenium precursor is equal to a time interval(T₂) for the pulse of the reagent gas.

Alternatively, the time interval for each of the pulses of the rutheniumprecursor and the reagent gas may have different durations. That is, theduration of the pulse of the ruthenium precursor may be shorter orlonger than the duration of the pulse of the reagent gas. For such anembodiment, a time interval (T₁) for the pulse of the rutheniumprecursor is different than the time interval (T₂) for the pulse of thereagent gas.

In addition, the periods of non-pulsing between each of the pulses ofthe ruthenium precursor and the reagent gas may have the same duration.That is, the duration of the period of non-pulsing between each pulse ofthe ruthenium precursor and each pulse of the reagent gas is identical.For such an embodiment, a time interval (T₃) of non-pulsing between thepulse of the ruthenium precursor and the pulse of the reagent gas isequal to a time interval (T₄) of non-pulsing between the pulse of thereagent gas and the pulse of the ruthenium precursor. During the timeperiods of non-pulsing only the constant carrier gas stream is providedto the process chamber.

Alternatively, the periods of non-pulsing between each of the pulses ofthe ruthenium precursor and the reagent gas may have different duration.That is, the duration of the period of non-pulsing between each pulse ofthe ruthenium precursor and each pulse of the reagent gas may be shorteror longer than the duration of the period of non-pulsing between eachpulse of the reagent gas and the ruthenium precursor. For such anembodiment, a time interval (T₃) of non-pulsing between the pulse of theruthenium precursor and the pulse of the reagent gas is different from atime interval (T₄) of non-pulsing between the pulse of the reagent gasand the pulse of ruthenium precursor. During the time periods ofnon-pulsing only the constant carrier gas stream is provided to theprocess chamber.

Additionally, the time intervals for each pulse of the rutheniumprecursor, the reagent gas and the periods of non-pulsing therebetweenfor each deposition cycle may have the same duration. For such anembodiment, a time interval (T₁) for the ruthenium precursor, a timeinterval (T₂) for the reagent gas, a time interval (T₃) of non-pulsingbetween the pulse of the ruthenium precursor and the pulse of thereagent gas and a time interval (T₄) of non-pulsing between the pulse ofthe reagent gas and the pulse of the ruthenium precursor each have thesame value for each deposition cycle. For example, in a first depositioncycle (C₁), a time interval (T₁) for the pulse of the rutheniumprecursor has the same duration as the time interval (T₁) for the pulseof the ruthenium precursor in subsequent deposition cycles (C₂ . . .C_(n)). Similarly, the duration of each pulse of the reagent gas and theperiods of non-pulsing between the pulse of the ruthenium precursor andthe reagent gas in the first deposition cycle (C₁) is the same as theduration of each pulse of the reagent gas and the periods of non-pulsingbetween the pulse of the ruthenium precursor and the reagent gas insubsequent deposition cycles (C₂ . . . C_(n)), respectively.

Alternatively, the time intervals for at least one pulse of theruthenium precursor, the reagent gas and the periods of non-pulsingtherebetween for one or more of the deposition cycles of the rutheniummaterial deposition process may have different durations. For such anembodiment, one or more of the time intervals (T₁) for the pulses of theruthenium precursor, the time intervals (T₂) for the pulses of thereagent gas, the time intervals (T₃) of non-pulsing between the pulse ofthe ruthenium precursor and the reagent gas and the time intervals (T₄)of non-pulsing between the pulses of the reagent gas and the rutheniumprecursor may have different values for one or more deposition cycles ofthe cyclical deposition process. For example, in a first depositioncycle (C₁), the time interval (T₁) for the pulse of the rutheniumprecursor may be longer or shorter than one or more time interval (T₁)for the pulse of the ruthenium precursor in subsequent deposition cycles(C₂ . . . C_(n)). Similarly, the durations of the pulses of the reagentgas and the periods of non-pulsing between the pulse of the rutheniumprecursor and the reagent gas in the first deposition cycle (C₁) may bethe same or different than the duration of each pulse of the reagent gasand the periods of non-pulsing between the pulse of the rutheniumprecursor and the reagent gas in subsequent deposition cycles (C₂ . . .C_(n)).

In some embodiments, a constant flow of a carrier gas or a purge gas maybe provided to the process chamber modulated by alternating periods ofpulsing and non-pulsing where the periods of pulsing alternate betweenthe ruthenium precursor and the reagent gas along with the carrier/purgegas stream, while the periods of non-pulsing include only thecarrier/purge gas stream.

A PE-ALD process chamber (e.g., process chamber 50) may be used to formmany materials including tantalum, tantalum nitride, titanium, titaniumnitride, ruthenium, tungsten, tungsten nitride and other materials. Inone embodiment, ruthenium material may be deposited on a barrier layercontaining tantalum and/or tantalum nitride, which may be formed duringan ALD process as described in commonly assigned U.S. Pat. No.6,951,804, which is incorporated herein in its entirety by reference.Further disclosure of processes for depositing a tungsten material on aruthenium material is further described in commonly assigned andco-pending U.S. Ser. No. 11/009,331, entitled “Ruthenium as anUnderlayer for Tungsten Film Deposition,” filed Dec. 10, 2004, andpublished as US 2006-0128150, which is incorporated herein in itsentirety by reference.

In one example, a copper seed layer may be formed on the rutheniummaterial by a CVD process and thereafter, bulk copper is deposited tofill the interconnect by an ECP process. In another example, a copperseed layer may be formed on the ruthenium material by a PVD process andthereafter, bulk copper is deposited to fill the interconnect by an ECPprocess. In another example, a copper seed layer may be formed on theruthenium material by an electroless process and thereafter, bulk copperis deposited to fill the interconnect by an ECP process. In anotherexample, the ruthenium material serves as a seed layer to which a copperbulk fill is directly deposited by an ECP process or an electrolessdeposition process.

In another example, a tungsten seed layer may be formed on the rutheniummaterial by an ALD process and thereafter, bulk tungsten is deposited tofill the interconnect by a CVD process or a pulsed-CVD process. Inanother example, a tungsten seed layer may be formed on the rutheniummaterial by a PVD process and thereafter, bulk tungsten is deposited tofill the interconnect by a CVD process or a pulsed-CVD process. Inanother example, a tungsten seed layer may be formed on the rutheniummaterial by an ALD process and thereafter, bulk tungsten is deposited tofill the interconnect by an ECP process. In another example, theruthenium material serves as a seed layer to which a tungsten bulk fillis directly deposited by a CVD process or a pulsed-CVD process.

Several integration sequence are conducted in order to form a rutheniummaterial within an interconnect. In one example, the subsequent stepsfollow: a) pre-clean of the substrate; b) deposition of a barrier layer(e.g., ALD of TaN); c) deposition of ruthenium by ALD; and d) depositionof seed copper by electroless, ECP or PVD followed by deposition of bulkcopper by ECP. In another example, the subsequent steps follow: a)deposition of a barrier layer (e.g., ALD of TaN); b) punch through step;c) deposition of ruthenium by ALD; and d) deposition of seed copper byelectroless, ECP or PVD followed by deposition of bulk copper by ECP. Inanother example, the subsequent steps follow: a) deposition of rutheniumby ALD; b) punch through step; c) deposition of ruthenium by ALD; and d)deposition of seed copper by electroless, ECP or PVD followed bydeposition of bulk copper by electroless, ECP or PVD. In anotherexample, the subsequent steps follow: a) deposition of ruthenium by ALD;b) punch through step; c) deposition of ruthenium by ALD; and d)deposition of copper by electroless or ECP. In another embodiment, thesubsequent steps follow: a) pre-clean of the substrate; b) deposition ofruthenium by ALD; and c) deposition of seed copper by electroless, ECPor PVD followed by deposition of bulk copper by ECP. In another example,the subsequent steps follow: a) deposition of a barrier layer (e.g., ALDof TaN); b) deposition of ruthenium by ALD; c) punch through step; d)deposition of ruthenium by ALD; and e) deposition of seed copper byelectroless, ECP or PVD followed by deposition of bulk copper by ECP. Inanother example, the subsequent steps follow: a) deposition of a barrierlayer (e.g., ALD of TaN); b) punch through step; c) deposition of abarrier layer (e.g., ALD of TaN); d) deposition of ruthenium by ALD; andd) deposition of seed copper by electroless, ECP or PVD; and e)deposition of bulk copper by ECP. In one example, the subsequent stepsfollow: a) pre-clean of the substrate; b) deposition of a barrier layer(e.g., ALD of TaN); c) deposition of ruthenium by ALD; and d) depositionof copper bulk by electroless or ECP.

The pre-clean steps include methods to clean or purify the via, such asthe removal of residue at the bottom of the via (e.g., carbon) orreduction of copper oxide to copper metal. Punch through steps include amethod to remove material (e.g., barrier layer) from the bottom of thevia to expose conductive layer, such as copper. Further disclosure ofpunch through steps is described in more detail in the commonlyassigned, U.S. Pat. No. 6,498,091, which is incorporated herein in itsentirety by reference. The punch through steps may be conducted within aprocess chamber, such as either a barrier chamber or a clean chamber. Inembodiments of the invention, clean steps and punch through steps areapplied to ruthenium barrier layers. Further disclosure of overallintegrated methods are described in more detail in the commonlyassigned, U.S. Pat. No. 7,049,226, which is incorporated herein in itsentirety by reference.

The pyrrolyl ruthenium precursors and deposition chemistries utilized inthe various embodiments provide further significant advantages. Thelayers formed by the present ruthenium methodologies and precursors,such as pyrrolyl ruthenium precursors, have high nucleation density anduniformity. This is believed to promote freedom from surface defectssuch as satellites or islands in the resulting ruthenium material, incontrast to layers deposited by prior art methods and where priormethods employ sole ruthenocene compounds.

The pyrrolyl ruthenium precursors used to form ruthenium materialsprovide little or no nucleation delay during the ALD process. Also, theruthenium material deposited has a low carbon concentration andtherefore a high electrical conductance.

Also, the pyrrolyl ruthenium precursor and the reagents are utilized invarious embodiments during the ALD processes to deposit a rutheniummaterial on a barrier layer, especially a tantalum nitride barrierlayer. Unlike other ALD processes that use ruthenocene, the presentruthenium methodologies and precursors are not limited with the need topre-treat the barrier layer prior to the deposition of a rutheniummaterial. Excess process steps, such as pretreatment steps, are avoidedby applying a pyrrolyl ruthenium precursor during an ALD process toreduce the overall throughput of the production line.

Further, ruthenium materials deposited with the present methodologies,especially when employing a pyrrolyl ruthenium precursor, have superioradhesion properties to barrier layers as well as dielectric materials.It is believe the superior adhesion at least in part is due to thehigher degree of uniformity and nucleation density, whereby a more levelsurface and fewer surface defects results. Furthermore, ruthenocenecompounds generally require a temperature above 400° C. in order tobecome adsorbed to a substrate surface needed during an ALD process.However, since the threshold of many low-k devices is around 400° C.,ruthenocene compounds are not desirable ruthenium precursors for ALDprocesses.

The ruthenium materials formed from a pyrrolyl ruthenium precursorduring the ALD processes as described herein generally have a sheetresistance of less than 2,000 Ω/sq, preferably, less than 1,000 Ω/sq,and more preferably, less than 500 Ω/sq. For example, a rutheniummaterial may have a sheet resistance within a range from about 10 Ω/sqto about 250 Ω/sq.

A “substrate surface,” as used herein, refers to any substrate ormaterial surface formed on a substrate upon which film processing isperformed during a fabrication process. For example, a substrate surfaceon which processing can be performed include materials such as silicon,silicon oxide, strained silicon, silicon on insulator (SOI), carbondoped silicon oxides, silicon nitride, doped silicon, germanium, galliumarsenide, glass, sapphire, and any other materials such as metals, metalnitrides, metal alloys, and other conductive materials, depending on theapplication. Barrier layers, metals or metal nitrides on a substratesurface include titanium, titanium nitride, tungsten nitride, tantalumand tantalum nitride. Substrates may have various dimensions, such as200 mm or 300 mm diameter wafers, as well as, rectangular or squarepanes. Unless otherwise noted, embodiments and examples described hereinare preferably conducted on substrates with a 200 mm diameter or a 300mm diameter, more preferably, a 300 mm diameter. Processes of theembodiments described herein deposit ruthenium materials on manysubstrates and surfaces. Substrates on which embodiments of theinvention may be useful include, but are not limited to semiconductorwafers, such as crystalline silicon (e.g., Si<100> or Si<111>), siliconoxide, strained silicon, silicon germanium, doped or undopedpolysilicon, doped or undoped silicon wafers and patterned ornon-patterned wafers. Substrates may be exposed to a pretreatmentprocess to polish, etch, reduce, oxidize, hydroxylate, anneal and/orbake the substrate surface.

“Atomic layer deposition” (ALD) or “cyclical deposition” as used hereinrefers to the sequential introduction of two or more reactive compoundsto deposit a layer of material on a substrate surface. The two, three ormore reactive compounds may alternatively be introduced into a reactionzone or process region of a process chamber. The reactive compounds maybe in a state of gas, plasma, vapor, fluid or other state of matteruseful for a vapor deposition process. Usually, each reactive compoundis separated by a time delay to allow each compound to adhere and/orreact on the substrate surface. In one aspect, a first precursor orcompound A is pulsed into the reaction zone followed by a first timedelay. Next, a second precursor or compound B is pulsed into thereaction zone followed by a second delay. Compound A and compound Breact to form a deposited material. During each time delay a purge gasis introduced into the process chamber to purge the reaction zone orotherwise remove any residual reactive compound or by-products from thereaction zone. Alternatively, the purge gas may flow continuouslythroughout the deposition process so that only the purge gas flowsduring the time delay between pulses of reactive compounds. The reactivecompounds are alternatively pulsed until a desired film thickness of thedeposited material is formed on the substrate surface. In eitherscenario, the ALD process of pulsing compound A, purge gas, pulsingcompound B and purge gas is a cycle. A cycle can start with eithercompound A or compound B and continue the respective order of the cycleuntil achieving a film with the desired thickness. In anotherembodiment, a first precursor containing compound A, a second precursorcontaining compound B and a third precursor containing compound C areeach separately pulsed into the process chamber. Alternatively, a pulseof a first precursor may overlap in time with a pulse of a secondprecursor while a pulse of a third precursor does not overlap in timewith either pulse of the first and second precursors. “Process gas” asused herein refers to a single gas, multiple gases, a gas containing aplasma, combinations of gas(es) and/or plasma(s). A process gas maycontain at least one reactive compound for a vapor deposition process.The reactive compounds may be in a state of gas, plasma, vapor, fluid orother state of matter useful for a vapor deposition process. Also, aprocess may contain a purge gas or a carrier gas and not contain areactive compound.

Experiments

The experiments in this section were conducted on substrates initiallyprepared by thermally growing a silicon dioxide layer with a thicknessof 3,000 Å. Subsequently, a tantalum nitride layer was deposited by anALD process with a thickness of 10 Å. A full description of thedeposition techniques are further discussed in commonly assigned U.S.Pat. No. 6,951,804, which is incorporated herein in its entirety byreference. The tantalum nitride film is a dielectric with a sheetresistance greater than about 20,000 Ω/sq.

The ALD experiments were completed in an ALD chamber, as describedabove, available from Applied Materials, Inc., located in Santa Clara,Calif. The chamber spacing (distance between the wafer and the top ofchamber body) was 230 mils (5.84 mm).

Experiment 1: (DMPD)₂Ru with constant flow of NH₃ and intermediateplasma—The ruthenium precursor used during this experiment wasbis(2,4-dimethylpentadienyl) ruthenium ((DMPD)₂Ru). During theexperiment, the pressure within the process chamber was maintained atabout 2 Torr and the substrate was heated to about 300° C. An ALD cycleincluded the following steps. A ruthenium precursor gas was formed bypassing a nitrogen carrier gas with a flow rate of about 500 sccmthrough an ampoule of (DMPD)₂Ru heated at a temperature of about 80° C.The substrate was exposed to the ruthenium precursor gas with a flowrate of about 500 sccm and ammonia gas with a flow rate of about 1,500sccm for about 3 seconds. The flow of the ruthenium precursor gas wasstopped while the flow of the ammonia gas was maintained during a purgestep. The purge step was conducted for about 2 seconds. Subsequently, aplasma was ignited to form an ammonia plasma from the ammonia gas whilemaintaining the flow rate. The RF generator, having the power output setto about 125 watts at 13.56 MHz, produced the plasma for about 4 secondsduring the plasma step. Thereafter, the plasma power was turned off andthe chamber was exposed to a second purge step of the ammonia gas with aconstant flow rate for about 2 seconds. The deposition process wasstopped after the repetition of about 140 ALD cycles. A layer ofruthenium material was deposited on the substrate with a thickness ofabout 5 Å. The data from the experiment was analyzed to determine noexistence of a nucleation delay and the average deposition rate wasabout 0.22 Å/cycle.

Experiment 2: (MeCp)(EtCp)Ru with constant flow of NH₃ and intermediateplasma—The ruthenium precursor used during this experiment wasmethylcyclopentadienyl ethylcyclopentadienyl ruthenium ((MeCp)(EtCp)Ru).During the experiment, the pressure within the process chamber wasmaintained at about 2 Torr and the substrate was heated to about 300° C.An ALD cycle included the following steps. A ruthenium precursor gas wasformed by passing a nitrogen carrier gas with a flow rate of about 500sccm through an ampoule of (MeCp)(EtCp)Ru heated at a temperature ofabout 80° C. The substrate was exposed to the ruthenium precursor gaswith a flow rate of about 500 sccm and ammonia gas with a flow rate ofabout 1,500 sccm for about 3 seconds. The flow of the rutheniumprecursor gas was stopped while the flow of the ammonia gas wasmaintained during a purge step. The purge step was conducted for about 2seconds. Subsequently, a plasma was ignited to form an ammonia plasmafrom the ammonia gas while maintaining the flow rate. The RF generator,having the power output set to about 125 watts at 13.56 MHz, producedthe plasma for about 4 seconds during the plasma step. Thereafter, theplasma power was turned off and the chamber was exposed to a secondpurge step of the ammonia gas with a constant flow rate for about 2seconds. The deposition process was stopped after the repetition ofabout 140 ALD cycles. A layer of ruthenium material was deposited on thesubstrate with a thickness of about 6 Å. The data from the experimentwas analyzed to determine the existence of a nucleation delay.

Experiment 3: (MeCp)(Pv)Ru with constant flow of NH₃ and intermediateplasma—The ruthenium precursor used during this experiment wasmethylcyclopentadienyl pyrrolyl ruthenium ((MeCp)(Py)Ru). During theexperiment, the pressure within the process chamber was maintained atabout 2 Torr and the substrate was heated to about 300° C. An ALD cycleincluded the following steps. A ruthenium precursor gas was formed bypassing a nitrogen carrier gas with a flow rate of about 500 sccmthrough an ampoule of (MeCp)(Py)Ru heated at a temperature of about 80°C. The substrate was exposed to the ruthenium precursor gas with a flowrate of about 500 sccm and ammonia gas with a flow rate of about 1,500sccm for about 3 seconds. The flow of the ruthenium precursor gas wasstopped while the flow of the ammonia gas was maintained during a purgestep. The purge step was conducted for about 2 seconds. Subsequently, aplasma was ignited to form an ammonia plasma from the ammonia gas whilemaintaining the flow rate. The RF generator, having the power output setto about 300 watts at 13.56 MHz, produced the plasma for about 4 secondsduring the plasma step. Thereafter, the plasma power was turned off andthe chamber was exposed to a second purge step of the ammonia gas with aconstant flow rate for about 2 seconds. The deposition process wasstopped after the repetition of about 140 ALD cycles. A layer ofruthenium material was deposited on the substrate with a thickness ofabout 49 Å. The data from the experiment was analyzed to determine noexistence of a nucleation delay and the average deposition rate wasabout 0.35 Å/cycle.

Experiment 4: (MeCp)(Pv)Ru with constant flow of N₂ and intermediateplasma—During the experiment, the pressure within the process chamberwas maintained at about 4 Torr and the substrate was heated to about350° C. An ALD cycle included the following steps. A ruthenium precursorgas was formed by passing a nitrogen carrier gas with a flow rate ofabout 500 sccm through an ampoule of (MeCp)(Py)Ru heated at atemperature of about 80° C. The substrate was exposed to the rutheniumprecursor gas with a flow rate of about 500 sccm and nitrogen gas with aflow rate of about 1,500 sccm for about 3 seconds. The flow of theruthenium precursor gas was stopped while the flow of the nitrogen gaswas maintained during a purge step. The purge step was conducted forabout 2 seconds. Subsequently, a plasma was ignited to form a nitrogenplasma from the nitrogen gas while maintaining the flow rate. The RFgenerator, having the power output set to about 500 watts at 13.56 MHz,produced the plasma for about 4 seconds during the plasma step.Thereafter, the plasma power was turned off and the chamber was exposedto a second purge step of the nitrogen gas with a constant flow rate forabout 2 seconds. The deposition process was stopped after the repetitionof about 140 ALD cycles. A layer of ruthenium material was deposited onthe substrate with a thickness of about 46 Å. The data from theexperiment was analyzed to determine no existence of a nucleation delayand the average deposition rate was about 0.33 Å/cycle.

Experiment 5: (MeCp)(Pv)Ru with constant flow of H₂ and intermediateplasma—During the experiment, the pressure within the process chamberwas maintained at about 4 Torr and the substrate was heated to about350° C. An ALD cycle included the following steps. A ruthenium precursorgas was formed by passing a nitrogen carrier gas with a flow rate ofabout 500 sccm through an ampoule of (MeCp)(Py)Ru heated at atemperature of about 80° C. The substrate was exposed to the rutheniumprecursor gas with a flow rate of about 500 sccm and hydrogen gas with aflow rate of about 1,500 sccm for about 3 seconds. The flow of theruthenium precursor gas was stopped while the flow of the hydrogen gaswas maintained during a purge step. The purge step was conducted forabout 2 seconds. Subsequently, a plasma was ignited to form a hydrogenplasma from the hydrogen gas while maintaining the flow rate. The RFgenerator, having the power output set to about 500 watts at 13.56 MHz,produced the plasma for about 4 seconds during the plasma step.Thereafter, the plasma power was turned off and the chamber was exposedto a second purge step of the hydrogen gas with a constant flow rate forabout 2 seconds. The deposition process was stopped after the repetitionof about 140 ALD cycles. A layer of ruthenium material was deposited onthe substrate with a thickness of about 45 Å. The data from theexperiment was analyzed to determine no existence of a nucleation delayand the average deposition rate was about 0.32 Å/cycle.

Experiment 6: (MeCp)(Pv)Ru with intermediate NH₃ plasma—During theexperiment, the pressure within the process chamber was maintained atabout 2 Torr and the substrate was heated to about 300° C. An ALD cycleincluded the following steps. A ruthenium precursor gas was formed bypassing a nitrogen carrier gas with a flow rate of about 500 sccmthrough an ampoule of (MeCp)(Py)Ru heated at a temperature of about 80°C. The substrate was exposed to the ruthenium precursor gas with a flowrate of about 500 sccm for about 3 seconds. The flow of the rutheniumprecursor gas was stopped and a nitrogen purge gas with a flow rate ofabout 500 sccm was administered into the chamber during a purge step.The purge step was conducted for about 2 seconds. Thereafter, an ammoniagas with a flow rate of about 1,500 sccm was administered into thechamber after stopping the flow of the nitrogen gas. Subsequently, aplasma was ignited to form an ammonia plasma from the ammonia gas whilemaintaining the flow rate. The RF generator, having the power output setto about 300 watts at 13.56 MHz, produced the plasma for about 4 secondsduring the plasma step. Thereafter, the flow of the ammonia gas and theplasma power were turned off. The chamber was exposed to a second purgestep of nitrogen gas with a flow rate of about 500 sccm for about 2seconds. The deposition process was stopped after the repetition ofabout 150 ALD cycles. A layer of ruthenium material was deposited on thesubstrate with a thickness of about 51 Å. The data from the experimentwas analyzed to determine no existence of a nucleation delay and theaverage deposition rate was about 0.34 Å/cycle.

Experiment 7: (MeCp)(Pv)Ru with intermediate N₂ plasma—During theexperiment, the pressure within the process chamber was maintained atabout 4 Torr and the substrate was heated to about 350° C. An ALD cycleincluded the following steps. A ruthenium precursor gas was formed bypassing a nitrogen carrier gas with a flow rate of about 500 sccmthrough an ampoule of (MeCp)(Py)Ru heated at a temperature of about 80°C. The substrate was exposed to the ruthenium precursor gas with a flowrate of about 500 sccm for about 3 seconds. The flow of the rutheniumprecursor gas was stopped and a nitrogen purge gas with a flow rate ofabout 500 sccm was administered into the chamber during a purge step.The purge step was conducted for about 2 seconds. Subsequently, a plasmawas ignited to form a nitrogen plasma from the nitrogen gas whilemaintaining the flow rate. The RF generator, having the power output setto about 500 watts at 13.56 MHz, produced the plasma for about 4 secondsduring the plasma step. Thereafter, the flow of the nitrogen gas and theplasma power were turned off. The chamber was exposed to a second purgestep of nitrogen gas with a flow rate of about 500 sccm for about 2seconds. The deposition process was stopped after the repetition ofabout 150 ALD cycles. A layer of ruthenium material was deposited on thesubstrate with a thickness of about 50 Å. The data from the experimentwas analyzed to determine no existence of a nucleation delay and theaverage deposition rate was about 0.33 Å/cycle.

Experiment 8: (MeCp)(Pv)Ru with intermediate H₂ plasma—During theexperiment, the pressure within the process chamber was maintained atabout 4 Torr and the substrate was heated to about 350° C. An ALD cycleincluded the following steps. A ruthenium precursor gas was formed bypassing a nitrogen carrier gas with a flow rate of about 500 sccmthrough an ampoule of (MeCp)(Py)Ru heated at a temperature of about 80°C. The substrate was exposed to the ruthenium precursor gas with a flowrate of about 500 sccm for about 3 seconds. The flow of the rutheniumprecursor gas was stopped and a nitrogen purge gas with a flow rate ofabout 500 sccm was administered into the chamber during a purge step.The purge step was conducted for about 2 seconds. Thereafter, a hydrogengas with a flow rate of about 1,500 sccm was administered into thechamber after stopping the flow of the nitrogen gas. Subsequently, aplasma was ignited to form a hydrogen plasma from the hydrogen gas whilemaintaining the flow rate. The RF generator, having the power output setto about 500 watts at 13.56 MHz, produced the plasma for about 4 secondsduring the plasma step. Thereafter, the flow of the hydrogen gas and theplasma power were turned off. The chamber was exposed to a second purgestep of nitrogen gas with a flow rate of about 500 sccm for about 2seconds. The deposition process was stopped after the repetition ofabout 150 ALD cycles. A layer of ruthenium material was deposited on thesubstrate with a thickness of about 48 Å. The data from the experimentwas analyzed to determine no existence of a nucleation delay and theaverage deposition rate was about 0.32 Å/cycle.

Other ALD Process

Embodiments of the invention provide methods for depositing a variety ofmetal-containing materials (e.g., tantalum or tungsten containingmaterials) on a substrate by a thermal ALD process or a PE-ALD processby utilizing process chamber 50 or lid assembly 100. In one example,tantalum nitride is deposited by sequentially exposing a substrate to atantalum precursor and a plasma during a PE-ALD process. In anotherexample, tungsten nitride is deposited by sequentially exposing asubstrate to a tungsten precursor and a plasma during a PE-ALD process.In other examples, metallic tantalum or metallic tungsten is depositedby sequentially exposing a substrate to a tantalum precursor or atungsten precursor and a plasma during a PE-ALD process.

Tantalum precursors useful during vapor deposition processes asdescribed herein include pentakis(dimethylamido) tantalum (PDMAT orTa(NMe₂)₅), pentakis(ethylmethylamido) tantalum (PEMAT or Ta[N(Et)Me]₅),pentakis(diethylamido) tantalum (PDEAT or Ta(NEt₂)₅,),ethylimido-tris(dimethylamido) tantalum ((EtN)Ta(NMe₂)₃),ethylimido-tris(diethylamido) tantalum ((EtN)Ta(NEt₂)₃),ethylimido-tris(ethylmethylamido) tantalum ((EtN)Ta[N(Et)Me]₃),tertiarybutylimido-tris(dimethylamido) tantalum (TBTDMT or(^(t)BuN)Ta(NMe₂)₃), tertiarybutylimido-tris(diethylamido) tantalum(TBTDET or (^(t)BuN)Ta(NEt₂)₃),tertiarybutylimido-tris(ethylmethylamido) tantalum (TBTEAT or(^(t)BuN)Ta[N(Et)Me]₃), tertiaryamylimido-tris(dimethylamido) tantalum(TAIMATA or (^(t)AmyIN)Ta(NMe₂)₃, wherein ^(t)Amyl is the tertiaryamylgroup (C₅H₁₁— or CH₃CH₂C(CH₃)₂—), tertiaryamylimido-tris(diethylamido)tantalum (TAIEATA or (^(t)AmyIN)Ta(NEt₂)₃,tertiaryamylimido-tris(ethylmethylamido) tantalum (TAIMATA or(^(t)AmyIN)Ta([N(Et)Me]₃), tantalum halides (e.g., TaF₅ or TaCl₅),derivatives thereof, or combinations thereof.

Tungsten precursors that may be useful during the vapor depositionprocesses as described herein include bis(tertiarybutylimido)bis(tertiarybutylamido) tungsten ((^(t)BuN)₂W(N(H)tBu)₂),bis(tertiarybutylimido) bis(dimethylamido) tungsten((^(t)BuN)₂W(NMe₂)₂), bis(tertiarybutylimido) bis(diethylamido) tungsten((^(t)BuN)₂W(NEt₂)₂), bis(tertiarybutylimido) bis(ethylmethylamido)tungsten ((^(t)BuN)₂W(NEtMe)₂), tungsten hexafluoride, derivativesthereof, or combinations thereof.

Nitrogen precursors that may be useful for forming a metal-containingmaterial during the vapor deposition processes as described hereininclude ammonia (NH₃), hydrazine (N₂H₄), methylhydrazine (Me(H)NNH₂),dimethyl hydrazine (Me₂NNH₂ or Me(H)NN(H)Me), tertiarybutylhydrazine(tBu(H)NNH₂), phenylhydrazine (C₆H₅(H)NNH₂), a nitrogen plasma source(e.g., N,N₂, N₂/H₂, NH₃, or a N₂H₄ plasma), 2,2′-azotertbutane(^(t)BuNN^(t)Bu), an azide source, such as ethyl azide (EtN₃),trimethylsilyl azide (Me₃SiN₃), derivatives thereof, plasmas thereof, orcombinations thereof.

A suitable reagent for forming a metal-containing material may be areducing gas and include hydrogen (e.g., H₂ or atomic-H), atomic-N,ammonia (NH₃), hydrazine (N₂H₄), silane (SiH₄), disilane (Si₂H₆),trisilane (Si₃H₈), tetrasilane (Si₄H₁₀), dimethylsilane (SiC₂H₈), methylsilane (SiCH₆), ethylsilane (SiC₂H₈), chlorosilane (ClSiH₃),dichlorosilane (Cl₂SiH₂), hexachlorodisilane (Si₂Cl₆), borane (BH₃),diborane (B₂H₆), triborane, tetraborane, pentaborane, triethylborane(Et₃B), derivatives thereof, plasmas thereof, or combinations thereof.

A carrier gas, a purge gas and a process gas may contain nitrogen,hydrogen, ammonia, argon, neon, helium, or combinations thereof. Aplasma may be ignited containing any of these gases. Preferably, aplasma precursor gas that may be useful for forming a metal-containingmaterial during the vapor deposition processes as described hereininclude nitrogen, hydrogen, ammonia, argon or combinations thereof. Inone example, a plasma contains nitrogen and hydrogen. In anotherexample, a plasma contains nitrogen and ammonia. In another example, aplasma contains ammonia and hydrogen.

Metal-containing materials that may be formed during thermal ALD orPE-ALD processes as described herein include tantalum, tantalum nitride,tungsten, tungsten nitride, titanium, titanium nitride, alloys thereof,derivatives thereof or combinations thereof. In one embodiment, ametal-containing material may be formed during a PE-ALD processcontaining a constant flow of a reagent gas while providing sequentialpulses of a metal precursor and a plasma. In another embodiment, ametal-containing material may be formed during another PE-ALD processthat provides sequential pulses of a metal precursor and a reagentplasma. In both of these embodiments, the reagent is generally ionizedduring the process. Also, the PE-ALD process provides that the plasmamay be generated external from the process chamber, such as by a remoteplasma generator (RPS) system, or preferably, the plasma may begenerated in situ a plasma capable ALD process chamber. During PE-ALDprocesses, a plasma may be generated from a microwave (MW) frequencygenerator or a radio frequency (RF) generator. For example, a plasma maybe ignited within process chamber 50 or with lid assembly 100. In apreferred example, an in situ plasma is generated by a RF generator. Inanother embodiment, a metal-containing material may be formed during athermal ALD process that provides sequential pulses of a metal precursorand a reagent.

The ALD process provides that the process chamber may be pressurized ata pressure within a range from about 0.1 Torr to about 80 Torr,preferably from about 0.5 Torr to about 10 Torr, and more preferably,from about 1 to about 5. Also, the chamber or the substrate may beheated to a temperature of less than about 500° C., preferably within arange from about 100° C. to about 450° C., and more preferably, fromabout 150° C. to about 400° C., for example, about 300° C. During PE-ALDprocesses, a plasma is ignited within the process chamber for an in situplasma process, or alternative, may be formed by an external source,such as a remote plasma generator (RPS) system. A plasma may begenerated a MW generator, but preferably by a RF generator. For example,a plasma may be ignited within process chamber 50 or with lid assembly100. The RF generator may be set at a frequency within a range fromabout 100 KHz to about 1.6 MHz. In one example, a RF generator, with afrequency of 13.56 MHz, may be set to have a power output within a rangefrom about 100 watts to about 1,000 watts, preferably, from about 250watts to about 600 watts, and more preferably, from about 300 watts toabout 500 watts. In one example, a RF generator, with a frequency of 400KHz, may be set to have a power output within a range from about 200watts to about 2,000 watts, preferably, from about 500 watts to about1,500 watts. A surface of substrate may be exposed to a plasma having apower per surface area value within a range from about 0.01 watts/cm² toabout 10.0 watts/cm², preferably, from about 0.05 watts/cm² to about 6.0watts/cm².

The substrate may be for example, a silicon substrate having aninterconnect pattern defined in one or more dielectric material layersformed thereon. In example, the substrate contains a barrier layerthereon, while in another example, the substrate contains a dielectricsurface. The process chamber conditions such as, the temperature andpressure, are adjusted to enhance the adsorption of the process gases onthe substrate so as to facilitate the reaction of the pyrrolyl metalprecursors and the reagent gas.

In one embodiment, the substrate may be exposed to a reagent gasthroughout the whole ALD cycle. The substrate may be exposed to a metalprecursor gas formed by passing a carrier gas (e.g., nitrogen or argon)through an ampoule of a metal precursor. The ampoule may be heateddepending on the metal precursor used during the process. In oneexample, an ampoule containing (MeCp)(Py)Ru may be heated to atemperature within a range from about 60° C. to about 100° C., such as80° C. The metal precursor gas usually has a flow rate within a rangefrom about 100 sccm to about 2,000 sccm, preferably, from about 200 sccmto about 1,000 sccm, and more preferably, from about 300 sccm to about700 sccm, for example, about 500 sccm. The metal precursor gas and thereagent gas may be combined to form a deposition gas. A reagent gasusually has a flow rate within a range from about 100 sccm to about3,000 sccm, preferably, from about 200 sccm to about 2,000 sccm, andmore preferably, from about 500 sccm to about 1,500 sccm. In oneexample, ammonia is used as a reagent gas with a flow rate of about1,500 sccm. The substrate may be exposed to the metal precursor gas orthe deposition gas containing the metal precursor and the reagent gasfor a time period within a range from about 0.1 seconds to about 8seconds, preferably, from about 1 second to about 5 seconds, and morepreferably, from about 2 seconds to about 4 seconds. The flow of themetal precursor gas may be stopped once the metal precursor is adsorbedon the substrate. The metal precursor may be a discontinuous layer,continuous layer or even multiple layers.

The substrate and chamber may be exposed to a purge step after stoppingthe flow of the metal precursor gas. The flow rate of the reagent gasmay be maintained or adjusted from the previous step during the purgestep. Preferably, the flow of the reagent gas is maintained from theprevious step. Optionally, a purge gas may be administered into theprocess chamber with a flow rate within a range from about 100 sccm toabout 2,000 sccm, preferably, from about 200 sccm to about 1,000 sccm,and more preferably, from about 300 sccm to about 700 sccm, for example,about 500 sccm. The purge step removes any excess metal precursor andother contaminants within the process chamber. The purge step may beconducted for a time period within a range from about 0.1 seconds toabout 8 seconds, preferably, from about 1 second to about 5 seconds, andmore preferably, from about 2 seconds to about 4 seconds. The carriergas, the purge gas and the process gas may contain nitrogen, hydrogen,ammonia, argon, neon, helium, or combinations thereof. In a preferredembodiment, the carrier gas contains nitrogen.

Thereafter, the flow of the reagent gas may be maintained or adjustedbefore igniting a plasma. The substrate may be exposed to the plasma fora time period within a range from about 0.1 seconds to about 20 seconds,preferably, from about 1 second to about 10 seconds, and morepreferably, from about 2 seconds to about 8 seconds. Thereafter, theplasma power was turned off. In one example, the reagent may be ammonia,nitrogen, hydrogen or a combination thereof to form an ammonia plasma, anitrogen plasma, a hydrogen plasma or a combined plasma. The reactantplasma reacts with the adsorbed metal precursor on the substrate to forma metal-containing material thereon. In one example, the reactant plasmais used as a reductant to form metallic ruthenium, tantalum, tungsten,titanium or alloys thereof. However, a variety of reactants may be usedto form metal-containing materials having a wide range of compositions.In one example, a boron-containing reactant compound (e.g., diborane) isused to form a metal-containing material containing boride. In anotherexample, a silicon-containing reactant compound (e.g., silane) is usedto form a metal-containing material containing silicide.

The process chamber was exposed to a second purge step to remove excessprecursors or contaminants from the previous step. The flow rate of thereagent gas may be maintained or adjusted from the previous step duringthe purge step. An optional purge gas may be administered into theprocess chamber with a flow rate within a range from about 100 sccm toabout 2,000 sccm, preferably, from about 200 sccm to about 1,000 sccm,and more preferably, from about 300 sccm to about 700 sccm, for example,about 500 sccm. The second purge step may be conducted for a time periodwithin a range from about 0.1 seconds to about 8 seconds, preferably,from about 1 second to about 5 seconds, and more preferably, from about2 seconds to about 4 seconds.

The ALD cycle may be repeated until a predetermined thickness of themetal-containing material is deposited on the substrate. Themetal-containing material may be deposited with a thickness less than1,000 Å, preferably less than 500 Å and more preferably from about 10 Åto about 100 Å, for example, about 30 Å. The processes as describedherein may deposit a metal-containing material at a rate of at least0.15 Å/cycle, preferably, at least 0.25 Å/cycle, more preferably, atleast 0.35 Å/cycle or faster. In another embodiment, the processes asdescribed herein overcome shortcomings of the prior art relative asrelated to nucleation delay. There is no detectable nucleation delayduring many, if not most, of the experiments to deposit themetal-containing materials.

In another embodiment, a metal-containing material may be formed duringanother PE-ALD process that provides sequentially exposing the substrateto pulses of a metal precursor and an active reagent, such as a reagentplasma. The substrate may be exposed to a metal precursor gas formed bypassing a carrier gas through an ampoule containing a metal precursor,as described herein. The metal precursor gas usually has a flow ratewithin a range from about 100 sccm to about 2,000 sccm, preferably, fromabout 200 sccm to about 1,000 sccm, and more preferably, from about 300sccm to about 700 sccm, for example, about 500 sccm. The substrate maybe exposed to the deposition gas containing the metal precursor and thereagent gas for a time period within a range from about 0.1 seconds toabout 8 seconds, preferably, from about 1 second to about 5 seconds, andmore preferably from about 2 seconds to about 4 seconds. The flow of themetal precursor gas may be stopped once the metal precursor is adsorbedon the substrate. The metal precursor may be a discontinuous layer,continuous layer or even multiple layers.

Subsequently, the substrate and chamber are exposed to a purge step. Apurge gas may be administered into the process chamber during the purgestep. In one aspect, the purge gas is the reagent gas, such as ammonia,nitrogen or hydrogen. In another aspect, the purge gas may be adifferent gas than the reagent gas. For example, the reagent gas may beammonia and the purge gas may be nitrogen, hydrogen or argon. The purgegas may have a flow rate within a range from about 100 sccm to about2,000 sccm, preferably, from about 200 sccm to about 1,000 sccm, andmore preferably, from about 300 sccm to about 700 sccm, for example,about 500 sccm. The purge step removes any excess metal precursor andother contaminants within the process chamber. The purge step may beconducted for a time period within a range from about 0.1 seconds toabout 8 seconds, preferably, from about 1 second to about 5 seconds, andmore preferably, from about 2 seconds to about 4 seconds. A carrier gas,a purge gas and a process gas may contain nitrogen, hydrogen, ammonia,argon, neon, helium or combinations thereof.

The substrate and the adsorbed metal precursor thereon may be exposed tothe reagent gas during the next step of the ALD process. Optionally, acarrier gas may be administered at the same time as the reagent gas intothe process chamber. The reagent gas may be ignited to form a plasma.The reagent gas usually has a flow rate within a range from about 100sccm to about 3,000 sccm, preferably, from about 200 sccm to about 2,000sccm, and more preferably, from about 500 sccm to about 1,500 sccm. Inone example, ammonia is used as a reagent gas with a flow rate of about1,500 sccm. The substrate may be exposed to the plasma for a time periodwithin a range from about 0.1 seconds to about 20 seconds, preferably,from about 1 second to about 10 seconds, and more preferably, from about2 seconds to about 8 seconds. Thereafter, the plasma power may be turnedoff. In one example, the reagent may be ammonia, nitrogen, hydrogen orcombinations thereof, while the plasma may be an ammonia plasma, anitrogen plasma, a hydrogen plasma or a combination thereof. Thereactant plasma reacts with the adsorbed metal precursor on thesubstrate to form a metal-containing material thereon. Preferably, thereactant plasma is used as a reductant to form metallic ruthenium,tantalum, tungsten, titanium or alloys thereof. However, a variety ofreactants may be used to form metal-containing materials having a widerange of compositions, as described herein.

The process chamber may be exposed to a second purge step to removeexcess precursors or contaminants from the process chamber. The flow ofthe reagent gas may have been stopped at the end of the previous stepand started during the purge step, if the reagent gas is used as a purgegas. Alternative, a purge gas that is different than the reagent gas maybe administered into the process chamber. The reagent gas or purge gasmay have a flow rate within a range from about 100 sccm to about 2,000sccm, preferably, from about 200 sccm to about 1,000 sccm, and morepreferably, from about 300 sccm to about 700 sccm, for example, about500 sccm. The second purge step may be conducted for a time periodwithin a range from about 0.1 seconds to about 8 seconds, preferably,from about 1 second to about 5 seconds, and more preferably, from about2 seconds to about 4 seconds.

The ALD cycle may be repeated until a predetermined thickness of themetal-containing material is deposited on the substrate. Themetal-containing material may be deposited with a thickness less than1,000 Å, preferably less than 500 Å and more preferably from about 10 Åto about 100 Å, for example, about 30 Å. The processes as describedherein may deposit a metal-containing material at a rate of at least0.15 Å/cycle, preferably, at least 0.25 Å/cycle, more preferably, atleast 0.35 Å/cycle or faster. In another embodiment, the processes asdescribed herein overcome shortcomings of the prior art relative asrelated to nucleation delay. There is no detectable nucleation delayduring many, if not most, of the experiments to deposit themetal-containing materials.

The time interval for the pulse of the metal precursor is variabledepending upon a number of factors such as, for example, the volumecapacity of the process chamber employed, the vacuum system coupledthereto and the volatility/reactivity of the reactants used during theALD process. For example, (1) a large-volume process chamber may lead toa longer time to stabilize the process conditions such as, for example,carrier/purge gas flow and temperature, requiring a longer pulse time;(2) a lower flow rate for the process gas may also lead to a longer timeto stabilize the process conditions requiring a longer pulse time; and(3) a lower chamber pressure means that the process gas is evacuatedfrom the process chamber more quickly requiring a longer pulse time. Ingeneral, the process conditions are advantageously selected so that apulse of the metal precursor provides a sufficient amount of precursorso that at least a monolayer of the metal precursor is adsorbed on thesubstrate. Thereafter, excess metal precursor remaining in the chambermay be removed from the process chamber by the constant carrier gasstream in combination with the vacuum system.

The time interval for each of the pulses of the metal precursor and thereagent gas may have the same duration. That is, the duration of thepulse of the metal precursor may be identical to the duration of thepulse of the reagent gas. For such an embodiment, a time interval (T₁)for the pulse of the metal precursor is equal to a time interval (T₂)for the pulse of the reagent gas.

Alternatively, the time interval for each of the pulses of the metalprecursor and the reagent gas may have different durations. That is, theduration of the pulse of the metal precursor may be shorter or longerthan the duration of the pulse of the reagent gas. For such anembodiment, a time interval (T₁) for the pulse of the metal precursor isdifferent than the time interval (T₂) for the pulse of the reagent gas.

In addition, the periods of non-pulsing between each of the pulses ofthe metal precursor and the reagent gas may have the same duration. Thatis, the duration of the period of non-pulsing between each pulse of themetal precursor and each pulse of the reagent gas is identical. For suchan embodiment, a time interval (T₃) of non-pulsing between the pulse ofthe metal precursor and the pulse of the reagent gas is equal to a timeinterval (T₄) of non-pulsing between the pulse of the reagent gas andthe pulse of the metal precursor. During the time periods of non-pulsingonly the constant carrier gas stream is provided to the process chamber.

Alternatively, the periods of non-pulsing between each of the pulses ofthe metal precursor and the reagent gas may have different duration.That is, the duration of the period of non-pulsing between each pulse ofthe metal precursor and each pulse of the reagent gas may be shorter orlonger than the duration of the period of non-pulsing between each pulseof the reagent gas and the metal precursor. For such an embodiment, atime interval (T₃) of non-pulsing between the pulse of the metalprecursor and the pulse of the reagent gas is different from a timeinterval (T₄) of non-pulsing between the pulse of the reagent gas andthe pulse of metal precursor. During the time periods of non-pulsingonly the constant carrier gas stream is provided to the process chamber.

Additionally, the time intervals for each pulse of the metal precursor,the reagent gas and the periods of non-pulsing therebetween for eachdeposition cycle may have the same duration. For such an embodiment, atime interval (T₁) for the metal precursor, a time interval (T₂) for thereagent gas, a time interval (T₃) of non-pulsing between the pulse ofthe metal precursor and the pulse of the reagent gas and a time interval(T₄) of non-pulsing between the pulse of the reagent gas and the pulseof the metal precursor each have the same value for each depositioncycle. For example, in a first deposition cycle (C₁), a time interval(T₁) for the pulse of the metal precursor has the same duration as thetime interval (T₁) for the pulse of the metal precursor in subsequentdeposition cycles (C₂ . . . C_(n)). Similarly, the duration of eachpulse of the reagent gas and the periods of non-pulsing between thepulse of the metal precursor and the reagent gas in the first depositioncycle (C₁) is the same as the duration of each pulse of the reagent gasand the periods of non-pulsing between the pulse of the metal precursorand the reagent gas in subsequent deposition cycles (C₂ . . . C_(n)),respectively.

Alternatively, the time intervals for at least one pulse of the metalprecursor, the reagent gas and the periods of non-pulsing therebetweenfor one or more of the deposition cycles of the metal-containingmaterial deposition process may have different durations. For such anembodiment, one or more of the time intervals (T₁) for the pulses of themetal precursor, the time intervals (T₂) for the pulses of the reagentgas, the time intervals (T₃) of non-pulsing between the pulse of themetal precursor and the reagent gas and the time intervals (T₄) ofnon-pulsing between the pulses of the reagent gas and the metalprecursor may have different values for one or more deposition cycles ofthe cyclical deposition process. For example, in a first depositioncycle (C₁), the time interval (T₁) for the pulse of the metal precursormay be longer or shorter than one or more time interval (T₁) for thepulse of the metal precursor in subsequent deposition cycles (C₂ . . .C_(n)). Similarly, the durations of the pulses of the reagent gas andthe periods of non-pulsing between the pulse of the metal precursor andthe reagent gas in the first deposition cycle (C₁) may be the same ordifferent than the duration of each pulse of the reagent gas and theperiods of non-pulsing between the pulse of the metal precursor and thereagent gas in subsequent deposition cycles (C₂ . . . C_(n)).

In some embodiments, a constant flow of a carrier gas or a purge gas maybe provided to the process chamber modulated by alternating periods ofpulsing and non-pulsing where the periods of pulsing alternate betweenthe metal precursor and the reagent gas along with the carrier/purge gasstream, while the periods of non-pulsing include only the carrier/purgegas stream.

While foregoing is directed to the preferred embodiment of theinvention, other and further embodiments of the invention may be devisedwithout departing from the basic scope thereof, and the scope thereof isdetermined by the claims that follow.

1. A plasma baffle assembly for receiving a process gas within aplasma-enhanced vapor deposition chamber, comprising: a plasma baffleplate containing an upper surface to receive a process gas and a lowersurface to emit the process gas; a plurality of openings configured toflow the process gas from above the upper surface to below the lowersurface, wherein each opening is positioned at a predetermined angle ofa vertical axis that is perpendicular to the lower surface; and aconical nose cone on the upper surface.
 2. The plasma baffle assembly ofclaim 1, wherein the plurality of openings is a plurality of slots. 3.The plasma baffle assembly of claim 1, wherein the predetermined angleis positioned to provide the process gas with a circular gas flowpattern.
 4. The plasma baffle assembly of claim 3, wherein the circulargas flow pattern comprises a flow pattern selected from the groupconsisting of vortex, helix, spiral, twirl, twist, coil, whirlpool, andderivatives thereof.
 5. The plasma baffle assembly of claim 2, whereinthe predetermined angle is within a range from about 20° to about 70°.6. The plasma baffle assembly of claim 5, wherein each slot of theplurality of slots has a width within a range from about 0.60 mm toabout 0.90 mm.
 7. The plasma baffle assembly of claim 6, wherein theplurality of slots comprises about 10 slots or more.
 8. The plasmabaffle assembly of claim 6, wherein each slot of the plurality of slotshas a width to prohibit back diffusion of gas or formation of asecondary plasma.
 9. The plasma baffle assembly of claim 2, wherein theplasma baffle plate comprises a conductive material selected from thegroup consisting of aluminum, stainless steel, steel, iron, chromium,nickel, alloys thereof, and combinations thereof.
 10. The plasma baffleassembly of claim 9, wherein each of the slots have an opening thatextends across the upper surface between the conical nose cone and anouter edge of the plasma baffle plate, and the opening extends at anangle measured from a radius of the upper surface.
 11. The plasma baffleassembly of claim 10, wherein the angle is tangential or substantiallytangential to a point along the radius, wherein a center of the uppersurface and the point are at a distance within a range from about 1 mmto about 3 mm.
 12. The plasma baffle assembly of claim 10, wherein theangle is tangential or substantially tangential to the conical nosecone.
 13. The plasma baffle assembly of claim 10, wherein the angle iswithin a range from about 20° to about 45°.
 14. The plasma baffleassembly of claim 9, wherein the conical nose cone has a flat uppersurface.
 15. The plasma baffle assembly of claim 9, wherein the conicalnose cone has a concave upper surface or a convex upper surface.
 16. Theplasma baffle assembly of claim 1, wherein the plurality of openings isa plurality of holes.
 17. The plasma baffle assembly of claim 16,wherein the predetermined angle is positioned to provide the process gastowards the vertical axis.
 18. The plasma baffle assembly of claim 17,wherein the predetermined angle is within a range from about 30° toabout 40°.
 19. The plasma baffle assembly of claim 16, wherein each holeof the plurality of holes has a diameter on the upper surface of theplasma baffle plate within a range from about 1.5 mm to about 2 mm and adiameter on the lower surface of the plasma baffle plate within a rangefrom about 0.6 mm to about 1 mm.
 20. The plasma baffle assembly of claim19, wherein the plurality of holes comprises about 4 holes or more. 21.The plasma baffle assembly of claim 1, wherein the plurality of openingscomprises a plurality of holes and a plurality of rounded holes.
 22. Aplasma baffle assembly for receiving a process gas within aplasma-enhanced vapor deposition chamber, comprising: a plasma baffleplate containing an upper surface to receive a process gas and a lowersurface to emit the process gas; and a plurality of openings configuredto flow the process gas from above the upper surface to below the lowersurface, wherein each opening is positioned at a predetermined angle notparallel from a perpendicular axis of the lower surface.
 23. A plasmabaffle assembly for receiving a process gas within a plasma-enhancedvapor deposition chamber, comprising: a plasma baffle plate containingan upper surface to receive a process gas and a lower surface to emitthe process gas; and a plurality of openings configured to flow theprocess gas from above the upper surface to below the lower surface,wherein each opening is positioned at a predetermined angle obscuredfrom a perpendicular axis of the lower surface.
 24. A showerheadassembly for receiving a process gas within a plasma-enhanced vapordeposition chamber, comprising: a showerhead plate containing an uppersurface to receive gases and a lower surface to emit the gases; an innerarea on the upper surface for receiving a first process gas, wherein theinner area comprises a first plurality of openings configured to flowthe first process gas from above the upper surface to below the lowersurface; and an outer area on the upper surface for receiving the secondprocess gas, wherein the outer area comprises a second plurality ofopenings configured to flow the second process gas from above the uppersurface to below the lower surface.
 25. A showerhead assembly forreceiving a process gas within a plasma-enhanced vapor depositionchamber, comprising: a showerhead plate containing an upper surface toreceive gases and a lower surface to emit the gases; an inner area onthe upper surface for receiving a first process gas, wherein the innerarea comprises at least one opening configured to flow the first processgas from above the upper surface to below the lower surface; an outerarea on the upper surface for receiving the second process gas, whereinthe outer area comprises a second plurality of openings configured toflow the second process gas from above the upper surface to below thelower surface; a cooling assembly positioned above and in contact withthe showerhead plate; an inner region between the inner area and thecooling assembly; and an outer region between the outer are and thecooling assembly.
 26. The showerhead assembly of claim 25, wherein thelower surface is shaped and sized to substantially cover a substratereceiving surface.
 27. The showerhead assembly of claim 26, wherein theinner region of the showerhead plate comprises a plasma baffle.
 28. Theshowerhead assembly of claim 27, wherein the plasma baffle is removablefrom the showerhead plate.
 29. The showerhead assembly of claim 27,wherein the showerhead plate comprises a conductive material selectedfrom the group consisting of aluminum, stainless steel, steel, iron,chromium, nickel, alloys thereof, and combinations thereof.
 30. Theshowerhead assembly of claim 25, wherein the second plurality ofopenings is a plurality of holes.
 31. The showerhead assembly of claim30, wherein each hole of the plurality of holes has a diameter within arange from about 0.20 mm to about 0.80 mm.
 32. The showerhead assemblyof claim 31, wherein the plurality of holes comprises about 1,000 holesor more.
 33. The showerhead assembly of claim 31, wherein each hole ofthe plurality of holes has a diameter to prohibit back diffusion of gasor formation of a secondary plasma.
 34. The showerhead assembly of claim25, wherein the cooling assembly comprises a plurality of passagewaysfor directing the second process gas into the outer region.
 35. Theshowerhead assembly of claim 34, wherein each passageway of theplurality of passageways extends into the outer region at apredetermined angle.
 36. The showerhead assembly of claim 35, whereinthe predetermined angle prohibits back diffusion of gas or formation ofa secondary plasma.
 37. The showerhead assembly of claim 35, wherein thepredetermined angle is within a range from about 15° to about 35°. 38.The showerhead assembly of claim 34, wherein each passageway of theplurality of passageways provides an obscured flow path for the secondprocess gas into the outer region.
 39. The showerhead assembly of claim34, wherein the plurality of passageways comprises at least about 10channels.
 40. The showerhead assembly of claim 25, wherein the at leastone opening comprises a first plurality of openings configured to flowthe first process gas from above the upper surface to below the lowersurface.
 41. The showerhead assembly of claim 40, wherein the firstplurality of openings is a plurality of slots.
 42. The showerheadassembly of claim 41, wherein the plurality of slots is positioned at apredetermined angle measured from a perpendicular axis of the lowersurface.
 43. The showerhead assembly of claim 42, wherein thepredetermined angle is within a range from about 20° to about 70°. 44.The showerhead assembly of claim 43, wherein each slot of the pluralityof slots has a width within a range from about 0.60 mm to about 0.90 mm.45. The showerhead assembly of claim 43, wherein the plurality of slotscomprises about 10 slots or more.
 46. The showerhead assembly of claim44, wherein each slot of the plurality of slots has a width to prohibitback diffusion of gas or formation of a secondary plasma.
 47. Ashowerhead assembly for conducting a vapor deposition process,comprising: a showerhead plate having a bottom surface to substantiallycover a substrate receiving surface within a process chamber; an innerregion of the showerhead plate for distributing a first process gasthrough a plurality of slots positioned at a predetermined injectionangle relative to the substrate receiving surface; and an outer regionof the showerhead plate for distributing a second process gas through aplurality of holes.